Ethylene-based polymers

ABSTRACT

The invention provides an ethylene-based polymer comprising the following properties: a) a ZSVR value from 1.2 to 2.6, b) a MWD from 1.5 to 2.8, and c) a tan delta (0.1 rad/s; 190 C) from 5.0 to 50.

REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. ProvisionalApplication No. 62/018,863, filed Jun. 30, 2014, and incorporated hereinby reference.

BACKGROUND

Ethylene-based polymers, such as, polyethylene is known for use in themanufacture of a wide a variety of articles. The polyethylenepolymerization process can be varied, in a number of ways to produce awide variety of resultant polyethylene resins, having different physicalproperties that render the various resins suitable for use in differentapplications. It is generally known that ethylene-based polymers can beproduced in solution phase loop reactors, in which ethylene monomer, andoptionally one or more alpha olefin comonomers, typically having from 3to 10 carbon atoms, are circulated in the presence of one or morecatalyst systems, under pressure, around a loop reactor, by acirculation pump. The ethylene monomers, and optionally one or morecomonomers, are present in a liquid diluent, such as an alkane orisoalkane. Hydrogen may also be added to the reactor. The catalystsystems for producing ethylene-based polymers may typically comprise achromium-based catalyst system, a Ziegler Natta catalyst system, and/ora molecular (either metallocene or non-metallocene) catalyst system.Despite the research efforts in developing ethylene-based polymers,there is still a need for new ethylene-based polymers having improvedproperties. These needs have been met by the following invention.

SUMMARY OF THE INVENTION

The instant invention provides an ethylene-based polymer comprising thefollowing properties:

-   -   a) a ZSVR value from 1.2 to 2.6,    -   b) a MWD from 1.5 to 2.8, and    -   c) a tan delta (0.1 rad/s; 190° C.) from 5.0 to 50.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts conventional GPC profiles for an inventive (Inventive9=Inventive 11) and two comparative (Comparative 3 and Comparative 4)ethylene-based polymers.

FIG. 2 depicts CEF (Crystallization Elution Fractionation—ComonomerDistribution) profiles for an inventive (Inventive 9=Inventive 11) andtwo comparative (Comparative 3 and Comparative 4) ethylene-basedpolymers.

FIG. 3 depicts Tan Delta profiles for one inventive (Inventive9=Inventive 11) and two comparative (Comparative 3 and Comparative 4)ethylene-based polymers.

DETAILED DESCRIPTION OF THE INVENTION

As discussed above, the invention provides an ethylene-based polymercomprising the following properties:

-   -   a) a ZSVR value from 1.2 to 2.6,    -   b) a MWD from 1.5 to 2.8, and    -   c) a tan delta (0.1 rad/s; 190° C.) from 5.0 to 50.

An ethylene-based polymer may comprise a combination of two or moreembodiments as described herein.

The MWD(=Mw/Mn) is measured according to conventional GPC method asdescribed below.

In one embodiment, the ethylene-based polymer has the followingproperties: d) a melt index (12) less than 0.9 g/10 min, further lessthan, or equal to, 0.8 g/10 min, further less than, or equal to, 0.6g/10 min; and a tan delta (0.1 rad/s; 190° C.) greater than 5.0, furthergreater than 6.0, further greater than 7.0. In a further embodiment, theethylene-based polymer has a melt index greater than, or equal to, 0.05,further greater than, or equal to, 0.1.

In one embodiment, the ethylene-based polymer has the followingproperties: e) a melt index (I2) greater than, or equal to, 0.9 g/10min, and a tan delta (0.1 rad/s; 190° C.) greater than 15, furthergreater than 20, further greater than 25; and a ZSVR value from 1.3 to2.6, further from 1.3 to 2.5, further from 1.3 to 2.3. In a furtherembodiment, the ethylene-based polymer has a melt index less than, orequal to, 10, further less than, or equal to, 5.0, further less than, orequal to, 2.0.

In one embodiment, the ethylene-based polymer is anethylene/alpha-olefin interpolymer.

In one embodiment, the ethylene-based polymer has a density from 0.885to 0.940 g/cc, further from 0.890 to 0.930 g/cc, further from 0.892 to0.920 g/cc (1 cc=1 cm³).

In one embodiment, the ethylene-based polymer has a melt index (12) from0.05 to 500 g/10 min, further from 0.05 to 100 g/10 min, further 0.1 to50 g/10 min, further from 0.1 to 20 g/10 min, further from 0.1 to 5 g/10min, further from 0.1 to 2 g/10 min.

In one embodiment, the ethylene-based polymer has a tan delta (0.1rad/s; 190° C.) from 5.0 to 50, further from 7.0 to 45, further from 8.0to 45.

In one embodiment, the ethylene-based polymer has a single peak in theCEF-Comonomer Distribution, at a temperature from 60° C. to 100° C.,further from 60° C. to 95° C.

In one embodiment, the ethylene-based polymer has a CEF profile that hasa single peak with a peak width at 25% peak height less than 30° C. (30degrees C.), less than 25° C. (25 degrees C.), less than 20° C. (20degrees C.), most preferably less than 15° C. (15 degrees C.).

In one embodiment, the ethylene-based polymer has a single peak in theCEF-Comonomer Distribution, at a temperature from 60° C. to 100° C., andwherein the peak has a peak width at 25% peak height less than 30° C.(30 degrees C.), less than 25° C. (25 degrees C.), less than 20° C. (20degrees C.), most preferably less than 15° C. (15 degrees C.).

In one embodiment, the ethylene-based polymer has a single peak in theCEF-Comonomer Distribution, at a temperature from 60° C. to 95° C., andwherein the peak has a peak width at 25% peak height less than 30° C.(30 degrees C.), less than 25° C. (25 degrees C.), less than 20° C. (20degrees C.), most preferably less than 15° C. (15 degrees C.).

An inventive ethylene-based polymer may comprise a combination of two ormore embodiments described herein.

The invention also provides a composition comprising an inventiveethylene-based polymer as described herein.

An inventive composition may comprise a combination of two or moreembodiments described herein.

The invention also provides an article comprising at least one componentformed from an inventive composition.

An inventive article may comprise a combination of two or moreembodiments described herein.

Ethylene-Based Polymers

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises, in polymerized form, a majority amount of ethylenemonomer (based on the weight of the polymer), and optionally maycomprise one or more comonomers. Trace amounts of impurities (forexample, catalyst residues) may be incorporated into and/or within thepolymer

The inventive ethylene based polymers, for example homopolymers(employed to refer to polymers prepared from only one type of monomer,with the understanding that trace amounts of impurities can beincorporated into the polymer structure), interpolymers, or copolymers,of ethylene, and optionally one or more comonomers, such as α-olefins,have a zero shear viscosity ratio (ZSVR) in the range from 1.2 to 2.6;or in the alternative, from 1.2 to 2.5; or in the alternative, from 1.3to 2.6; or in the alternative, from 1.3 to 2.6; or in the alternative,from 1.3 to 2.3; or in the alternative, from 1.3 to 2.2; or in thealternative, from 1.3 to 2.1.

The term “ethylene-based interpolymer,” as used herein, refers to apolymer that comprises a majority amount of polymerized ethylene monomer(based on weight of the polymer), and at least one comonomer, forexample, and α-olefin.

The term “ethylene-based copolymer,” as used herein, refers to a polymerthat comprises a majority amount of polymerized ethylene monomer (basedon weight of the polymer), and one comonomer (e.g., an α-olefin), as theonly two monomer types.

The term “ethylene/α-olefin interpolymer,” as used herein, refers to aninterpolymer that comprises a majority amount of polymerized ethylenemonomer (based on the weight of the interpolymer) and at least oneα-olefin.

The term, “ethylene/α-olefin copolymer,” as used herein, refers to acopolymer that comprises a majority amount of polymerized ethylenemonomer (based on the weight of the copolymer), and an α-olefin, as theonly two monomer types.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a density in the rangefrom 0.885 to 0.940 g/cm³. All individual values and subranges from0.885 to 0.940 g/cm³ are included herein and disclosed herein; forexample, the density can be from a lower limit of 0.885, 0.888, 0.890 or0.894 g/cm³, to an upper limit of 0.940, 0.938, 0.935, 0.932, 0.930,0.928, 0.925, 0.922, 0.920, 0.918, 0.915, 0.912, 0.910, or 0.905 g/cm³.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a molecular weightdistribution (M_(w)/M_(n)) (measured according to the conventional GPCmethod) in the range from 1.5 to 2.8; for example, the molecular weightdistribution (M_(w)/M_(n)) may be in the range from 1.5 to 2.7; or inthe alternative, the molecular weight distribution (M_(w)/M_(n)) may bein the range from 1.5 to 2.6; or in the alternative, from 1.6 to 2.7; orin the alternative, from 1.6 to 2.6; or in the alternative, from 1.6 to2.5; or in the alternative, from 1.7 to 2.7; or in the alternative, from1.7 to 2.6; or in the alternative, from 1.7 to 2.5; or in thealternative, from 1.7 to 2.2.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a weight averagemolecular weight (M_(w)) in the range from equal to, or greater than,20,000 g/mole, for example, in the range from 20,000 to 350,000 g/moles,further from 50,000 to 300,000 g/mole, further from 80,000 to 250,000g/mole, further from 90,000 to 200,000 g/mole.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a melt index (I₂) in therange from 0.05 to 500 g/10 minutes. All individual values and subrangesfrom 0.05 to 500 g/10 minutes are included herein and disclosed herein;for example, the melt index (I₂) can be from a lower limit of 0.05, 0.1,0.5, 0.2, 0.5, 1, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 10, 15, 20,30, 40, 50, 60, 80, 90, 100, or 150 g/10 minutes, to an upper limit of0.9, 1, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 10, 15, 20, 30, 40, 50,60, 80, 90, 100, 200, or 500 g/10 minutes.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a melt flow ratio(I₁₀/I₂) in the range of from 5.0 to 10. All individual values andsubranges from 5 to 10 are included herein and disclosed herein; forexample, the melt flow ratio (I₁₀/I₂) can be from a lower limit of 5.0,5.2, 5.3, 5.4 or 5.5, to an upper limit of 7.0, 7.5, 7.8, 8.0, 8.2, 8.5,9.0, or 10.

In one embodiment, the ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, have a long chain branchingfrequency in the range of from 0 to 3 long chain branches (LCB) per 1000C.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers, or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, may further comprise at least0.01 parts by weight of metal residues and/or metal oxide residuesremaining from the inventive catalyst system per one million parts ofthe inventive ethylene based polymers. The metal residues and/or metaloxide residues remaining from the catalyst system in the inventiveethylene based polymers may be measured by X-ray fluorescence (XRF),which is calibrated to reference standards.

The inventive ethylene-based polymers, such as interpolymers orcopolymers of ethylene, and optionally one or more comonomers, such asα-olefins, may comprise less than 48 percent by weight of units derivedfrom one or more α-olefin comonomers, based on the weight of thepolymer. All individual values and subranges from less than 48 weightpercent are included herein and disclosed herein; for example, theinventive ethylene based polymers may comprise from less than 37 percentby weight of units derived from one or more α-olefin comonomers; or inthe alternative, less than 30 percent by weight of units derived fromone or more α-olefin comonomers; or in the alternative, less than 23percent by weight of units derived from one or more α-olefin comonomers;and at least 0 percent by weight of units derived by α-olefincomonomers; or in the alternative, at least 1.3 percent by weight ofunits derived by α-olefin comonomers; or in the alternative, at least2.8 percent by weight of units derived by α-olefin comonomers; or in thealternative, at least 9.5 percent by weight of units derived by α-olefincomonomers.

In one embodiment, the ethylene-based polymer is anethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefincopolymer. Suitable alpha-olefins are described below.

The inventive ethylene-based polymers, such as interpolymers orcopolymers of ethylene, and optionally one or more comonomers, such asα-olefins, may comprise less than 20 percent by moles of units derivedfrom one or more α-olefin comonomers, based on the total moles ofpolymerized monomer units in the polymer. All individual values andsubranges from less than 20 mole percent are included herein anddisclosed herein; for example, the inventive ethylene based polymers maycomprise from less than 13 percent by moles of units derived from one ormore α-olefin comonomers; or in the alternative, from less than 9.5percent by moles of units derived from one or more α-olefin comonomers;or in the alternative, from less than 7.0 percent by moles of unitsderived from one or more α-olefin comonomers; and at least 0 percent bymoles of units derived by α-olefin comonomers; or in the alternative, atleast 0.3 percent by moles of units derived by α-olefin comonomers; orin the alternative, at least 0.7 percent by moles of units derived byα-olefin comonomers; or in the alternative, at least 2.5 percent bymoles of units derived by α-olefin comonomers.

The α-olefin comonomers typically have no more than 20 carbon atoms. Forexample, the α-olefin comonomers may preferably have 3 to 10 carbonatoms, and more preferably 3 to 8 carbon atoms. Exemplary α-olefincomonomers include, but are not limited to, propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and4-methyl-1-pentene. The one or more α-olefin comonomers may, forexample, be selected from the group consisting of propylene, 1-butene,1-hexene, and 1-octene; or in the alternative, from the group consistingof 1-hexene and 1-octene.

In one embodiment, the inventive ethylene-based polymers, for examplehomopolymers, interpolymers or copolymers, of ethylene, and optionallyone or more comonomers, such as α-olefins, may comprise at least 52percent by weight of units derived from ethylene, based on the weight ofthe polymer. All individual values and subranges from at least 52 weightpercent are included herein and disclosed herein; for example, theinventive ethylene based polymers may comprise at least 63 percent byweight of units derived from ethylene; or in the alternative, at least70 percent by weight of units derived from ethylene; or in thealternative, at least 77 percent by weight of units derived fromethylene; or in the alternative, at least 85 percent by weight of unitsderived from ethylene; and at most 100 percent by weight of unitsderived by ethylene; or in the alternative, at most 98.7 percent byweight of units derived by ethylene; or in the alternative, at most 97.2percent by weight of units derived by ethylene; or in the alternative,at most 90.5 percent by weight of units derived by ethylene,

The inventive ethylene-based polymers, for example homopolymers,interpolymers or copolymers, of ethylene, and optionally one or morecomonomers, such as α-olefins, may further comprise one or moreadditives. Such additives include, but are not limited to, antistaticagents, color enhancers, dyes, lubricants, pigments, primaryantioxidants, secondary antioxidants, processing aids, UV stabilizers,and combinations thereof. The inventive ethylene based polymers maycontain any amounts of additives. The inventive ethylene-based polymersmay comprise from about 0 to about 10 percent, further from 0.1 to 10percent, by the combined weight of such additives, based on the weightof the inventive ethylene based polymers and the one or more additives.The inventive ethylene-based polymers may further compromise fillers,which may include, but are not limited to, organic or inorganic fillers.Such fillers, e.g., calcium carbonate, talc, Mg(OH)₂, can be present inlevels from about 0 to about 20 percent, further from 1 to 20 percent,based on the weight of the inventive ethylene-based polymers and the oneor more additives and/or fillers. The inventive ethylene-based polymersmay further be blended with one or more polymers to form a blend.

The inventive ethylene-based polymer may comprise a combination of twoor more embodiments as described herein.

The inventive ethylene-based polymers are preferably produced usingsolution polymerization processes, using one or more reactors, such asloop reactors, isothermal reactors, stirred tank reactors, batchreactors in parallel, series, and/or any combinations thereof.

In general, the solution phase polymerization process occurs in one ormore well-stirred reactors such as one or more loop reactors or one ormore spherical isothermal reactors at a temperature in the range of from120° C. to 300° C.; for example, from 120 or 130 or 135 or 140 or 145 or150 or 155 or 160° C., to 150 or 155 or 165 or 170 or 175 or 180 or 185or 190 or 195 or 200 or 205 or 210 or 215 or 220 or 230 or 240 or 250°C.; and at pressures in the range of from 300 to 1500 psi; for example,from 400 to 750 psi. The solution phase polymerization process alsooccurs in one or more well-stirred reactors, such as one or more loopreactors, or one or more spherical isothermal reactors, with a reactorethylene exit concentration in the range of from 18 g/L to 1 g/L; forexample, from 18 or 16 or 14 or 12 or 10 or 8 or 6 g/L, to 11 or 9 or 7or 5 or 3 or 1 g/L. The residence time in solution phase polymerizationprocess is typically in the range from 2 to 30 minutes; for example,from 10 to 20 minutes. Ethylene, one or more solvents, one or morecatalyst systems, e.g., a catalyst system comprising the procatalyst ofFormula I, optionally one or more cocatalysts, and optionally one ormore comonomers are fed continuously to the one or more reactors.Exemplary solvents include, but are not limited to, isoparaffins. Forexample, such solvents are commercially available under the name ISOPARE from ExxonMobil Chemical Co., Houston, Tex. The resultant mixture ofthe ethylene based polymer and solvent is then removed from the reactor,and the ethylene based polymer is isolated. Solvent is typicallyrecovered via a solvent recovery unit, i.e., heat exchangers and vaporliquid separator drum, and is then recycled back into the polymerizationsystem.

In one embodiment, the ethylene based polymer may be produced, viasolution polymerization, in a dual reactor system, for example, a dualloop reactor system, wherein ethylene, and optionally one or moreα-olefins, are polymerized in the presence of the catalyst systemcomprising the procatalyst of Formula I, as described herein, andoptionally one or more cocatalysts. In one embodiment, the ethylenebased polymer may be produced via solution polymerization, in a dualreactor system, for example a dual loop reactor system, whereinethylene, and optionally one or more α-olefins, are polymerized in thepresence of the catalyst system, comprising the procatalyst of FormulaI, as described herein, and optionally one or more other catalysts. Thecatalyst system, as described herein, can be used in the first reactor,or second reactor, optionally in combination with one or more othercatalysts. In one embodiment, the ethylene based polymer may be producedvia solution polymerization in a dual reactor system, for example a dualloop reactor system, wherein ethylene, and optionally one or moreα-olefins, are polymerized in the presence of the catalyst system,comprising the procatalyst of Formula I, as described herein, in bothreactors.

The procatalyst comprising the metal-ligand complex of Formula I may beactivated, to form an active catalyst composition, by combination withone or more cocatalysts, as described herein, for example, a cationforming cocatalyst, a strong Lewis acid, or a combination thereof.Suitable cocatalysts for use include polymeric or oligomericaluminoxanes, especially methyl aluminoxane, as well as inert,compatible, noncoordinating, ion forming compounds. Exemplary suitablecocatalysts include, but are not limited to modified methyl aluminoxane(MMAO), bis(hydrogenated tallow alkyl)methyl,tetrakis(pentafluorophenyl)borate(1-)amine, triethyl aluminum (TEA), andcombinations thereof.

In another embodiment, the inventive ethylene based polymers, forexample homopolymers, interpolymers, or copolymers, of ethylene, andoptionally one or more comonomers, such as α-olefins, may be producedvia solution polymerization in a single reactor system, for example asingle loop reactor system, wherein ethylene, and optionally one or moreα-olefins, are polymerized in the presence of one or more catalystsystems.

As discussed above, in one embodiment, the ethylene-based polymer isformed by a process comprising polymerizing at least ethylene, in thepresence of at least one catalyst system comprising the reaction productof the following:

A) at least one cocatalyst; and

B) a procatalyst comprising a metal-ligand complex of Formula (I):

wherein:

M is titanium, zirconium, or hafnium, each independently being in aformal oxidation state of +2, +3, or +4; and n is an integer from 0 to3, and wherein when n is 0, X is absent; and

Each X, independently, is a (C₁-C₄₀)hydrocarbyl, a(C₁-C₄₀)heterohydrocarbyl, or a halide, and wherein each X,independently, is a monodentate ligand that is neutral, monoanionic, ordianionic; or

wherein two Xs are taken together to form a bidentate ligand that isneutral, monoanionic, or dianionic; and

wherein X and n are chosen, in such a way, that the metal-ligand complexof Formula (I) is, overall, neutral; and

Each Z independently is an oxygen atom, a sulfur atom,—NR[C₁-C₄₀)hydrocarbyl]-, or —P[(C₁-C₄₀)hydrocarbyl]-; and

L is a substituted or unsubstituted (C₁-C₄₀)hydrocarbylene, or asubstituted or unsubstituted (C₁-C₄₀)heterohydrocarbylene, and

wherein, for L, the (C₁-C₄₀)hydrocarbylene has a portion that comprisesa 1-carbon atom to 10-carbon atom linker backbone linking R²¹ and R²² inFormula (I) (to which L is bonded), or

wherein, for L, the (C₁-C₄₀)heterohydrocarbylene has a portion thatcomprises a 1-atom to 10-atom linker backbone linking R²¹ and R²² inFormula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atomlinker backbone of the (C₁-C₄₀)heterohydrocarbylene, independently, isone of the following: i) a carbon atom, ii) a heteroatom, wherein eachheteroatom independently is —O—or —S—, or iii) a substituent selectedfrom —S(O)—, —S(O)₂—, —Si(R^(C))₂—, —Ge(R^(C))₂—, —P(R^(C))—, or—N(R^(C))—, and wherein each R^(C) is, independently, a substituted orunsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁-C₃₀) heterohydrocarbyl; and

R²¹ and R²² are each, independently, C or Si; and

R¹ through R²⁰ are each, independently, selected from the groupconsisting of the following: a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)hetero-hydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, and a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and

wherein, when R¹⁷ is a hydrogen atom, then R¹⁸ is a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or

wherein, when R¹⁸ is a hydrogen atom, then R¹⁷ is a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and/or wherein,when R¹⁹ is a hydrogen atom, then R²⁰ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or

wherein, when R²⁰ is a hydrogen atom, then R¹⁹ is a substituted orunsubstituted (C₁ -C₄₀)hydrocarbyl, a substituted or unsubstituted (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and

wherein, for Formula I, two or more of R¹ through R²², optionally, mayform one or more ring structures, and wherein each ring structure hasfrom 3 to 50 atoms in the ring, excluding any hydrogen atoms; and

wherein, for Formula I, one or more hydrogen atoms may optionally besubstituted with one or more deuterium atoms.

The procatalyst of Formula I may comprise a combination of two or moreembodiments as described herein.

As used herein, R1=R¹, R2=R², R3=R³, and so forth. As known in the art,O is oxygen, S is sulfur, Si is silicon, and so forth.

In one embodiment, for Formula I, when R¹⁷ is a hydrogen atom, then R¹⁸is a substituted or unsubstituted (C₁-C₄₀)hydrocarbyl, a substituted orunsubstituted (C₁-C₄₀)heterohydro-carbyl, —Si(R^(C))₃, —Ge(R^(C))₃,—P(R^(C))₂, —N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C),—S(O)₂R^(C), —N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C),—C(O)N(R^(C))₂, or a halogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or

wherein, when R¹⁸ is a hydrogen atom, then R¹⁷ is a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,or a halogen atom; and wherein each R^(C) is independently a substitutedor unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁-C₃₀) heterohydrocarbyl; and/or

wherein, when R¹⁹ is a hydrogen atom, then R²⁰ is a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,or a halogen atom; and wherein each R^(C) is independently a substitutedor unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁-C₃₀) heterohydrocarbyl; or

wherein, when R²⁰ is a hydrogen atom, then R¹⁹ is a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,or a halogen atom; and wherein each R^(C) is independently a substitutedor unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁-C₃₀) heterohydrocarbyl.

In one embodiment, for Formula I, each Z is an oxygen atom.

In one embodiment, for Formula I, R²¹ and R²² are each C (carbon).

In one embodiment, each X is, independently, a (C₁-C₄₀)hydrocarbyl, a(C₁-C₄₀)hetero-hydrocarbyl, or a halide. In a further embodiment both Xgroups are the same.

In one embodiment, each X is, independently, a (C₁-C₄₀)hydrocarbyl, or ahalide. In a further embodiment both X groups are the same.

In one embodiment, each X is, independently, a (C₁-C₄₀)hydrocarbyl. In afurther embodiment both X groups are the same.

In one embodiment, each X is, independently, a (C₁-C₃)alkyl, furtherethyl or methyl, and further methyl. In a further embodiment both Xgroups are the same.

In one embodiment, for Formula I, L is selected from the following:—CH2CH2CH2-, —CH2CH2- or —CH2-; and further —CH2CH2- or —CH2- , andfurther —CH2-.

In one embodiment, for Formula I, each (C₁-C₄₀)hydrocarbyl, and each(C₁-C₄₀)hetero-hydrocarbyl is not substituted.

In one embodiment, for Formula I, at least one (C₁-C₄₀)hydrocarbyl,and/or at least one (C₁-C₄₀)hetero-hydrocarbyl is/are, independently,substituted with at least on R^(S) substituent, and wherein each R^(S)substituent is, independently, selected from the following: a halogenatom, a polyfluoro substituent, a perfluoro substituent, F₃C—, FCH₂O—,F₂HCO—, F₃CO—, (R^(C))₃Si—, (R^(C))₃Ge, (R^(C))O—, (R^(C))S—,(R^(C))S(O)—, (R^(C))S(O)₂—, (R^(C))₂P—, (R^(C))₂N—, (R^(C))₂C═N—, NC—,(R^(C))C(O)O—, (R^(C))OC(O)—, (R^(C))C(O)N(R^(C))—, or (R^(C))₂NC(O)—;and wherein each R^(C) is independently a substituted or unsubstituted(C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted (C₁-C₃₀)heterohydrocarbyl.

In one embodiment, for Formula I, each (C₁-C₄₀)hydrocarbyl, and each(C₁-C₄₀)hetero-hydrocarbyl are, independently, substituted with at leaston R^(S) substituent, and wherein each R^(S) substituent is,independently, selected from the following: a halogen atom, a polyfluorosubstituent, a perfluoro substituent, F₃C—, FCH₂O—, F₂HCO—, F₃CO—,(R^(C))₃Si—, (R^(C))₃Ge, (R^(C))O, (R^(C))S—, (R^(C))S(O)—,(R^(C))S(O)₂—, (R^(C))₂P—, (R^(C))₂N—, (R^(C))₂C═N—, NC—, (R^(C))C(O)O—,(R^(C))OC(O)—, (R^(C))C(O)N(R^(C))—, or (R^(C))₂NC(O)—; and wherein eachR^(C) is independently a substituted or unsubstituted(C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted (C₁-C₃₀)heterohydro-carbyl.

In one embodiment, two or more of R¹ to R²² do not form one or more ringstructures.

In one embodiment, Formula I does not contain one or more deuteriumatoms.

In one embodiment, for Formula I, the procatalyst is selected from thegroup consisting of the following I1 through I76:

In a further embodiment, for Formula I, the procatalyst is selected fromthe group consisting of the following: from I1 through I20, further fromI1 to I12, further from I1 to I6.

In one embodiment, for Formula I, R², R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹², R¹³and R¹⁵ are each hydrogen.

In one embodiment, for Formula I, M is zirconium or hafnium; n is 2;each X, independently, is a (C₁-C₄₀)hydrocarbyl, a(C₁-C₄₀)hetero-hydrocarbyl, or a halide; and R², R⁴, R⁵, R⁷, R⁸, R⁹,R¹⁰, R¹², R¹³ and R¹⁵ are each hydrogen.

In one embodiment, for Formula I, M is zirconium; and each Z is anoxygen atom.

In one embodiment, for Formula I, R¹ and R¹⁶ are each independentlyselected from the following i) through v):

In a further embodiment, both R¹ and R¹⁶ are the same. In each ofstructures 1) through v), the dashed line (---) indicated the point ifattachment to the remainder structure of Formula I.

In one embodiment, for Formula I, R¹ and R¹⁶ are each independentlyselected from the following i) through ii). In a further embodiment,both R¹ and R¹⁶ are the same.

In embodiment, for Formula I, R¹⁷ or R¹⁸ is a hydrogen atom, and theother is a substituted or unsubstituted (C₁-C₄₀)hydrocarbyl, asubstituted or unsubstituted (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(C))₂, —N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃,—S(O)R^(C), —S(O)₂R^(C), —N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C),—N(R)C(O)R^(C), —C(O)N(R^(C))₂, or a a halogen atom; and wherein eachR^(C) is independently a substituted or unsubstituted(C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted (C₁-C₃₀)heterohydrocarbyl. In a further embodiment, R¹⁹ or R²⁰ is a hydrogenatom, and the other is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,or a halogen atom; and wherein each R^(C) is independently a substitutedor unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁ -C₃₀) heterohydrocarbyl.

In one embodiment, R¹⁷ or R¹⁸ is hydrogen, and the other is anunsubstituted hydrocarbyl. In a further embodiment, R¹⁹ or R²° ishydrogen, and the other is an unsubstituted hydrocarbyl.

In one embodiment, for Formula I, R¹⁷, R¹⁸, R¹⁹ and R²° are each,independently, an unsubstituted (C₁-C₄₀)hydrocarbyl. In a furtherembodiment, R¹⁷, R¹⁸, R¹⁹ and R²⁰ are each, independently, anunsubstituted (C₁-C₃₀)hydrocarbyl, further an unsubstituted(C₁-C₂₀)hydrocarbyl, further an unsubstituted (C₁-C₁₀)hydrocarbyl,further an unsubstituted (C₁-C₅)hydrocarbyl, and further anunsubstituted (C₁-C₃)hydrocarbyl.

In one embodiment, for Formula I, R³ and R¹⁴ are each, independently, anunsubstituted (C₁-C₄₀)hydrocarbyl. In a further embodiment, R³ and R¹⁴are each, independently, an unsubstituted (C₁-C₃₀)hydrocarbyl, furtheran unsubstituted (C₁-C₂₀)hydrocarbyl, further an unsubstituted(C₁-C₁₀)hydrocarbyl, further an unsubstituted (C₁-C₅)hydrocarbyl, andfurther an unsubstituted (C₁-C₃)hydrocarbyl.

In one embodiment, for Formula I, R⁶ and R¹¹ are each, independently, anunsubstituted (C₁-C₄₀)hydrocarbyl or a halogen. In a further embodiment,R⁶ and R¹¹ are each, independently, an unsubstituted(C₁-C₃₀)hydrocarbyl, further an unsubstituted (C₁-C₂₀)hydrocarbyl,further an unsubstituted (C₁-C₁₀)hydrocarbyl, further an unsubstituted(C₁-C₅)hydrocarbyl, and further an unsubstituted (C₁-C₃)hydrocarbyl. Inanother embodiment, for Formula I, R⁶ and R¹¹ are each, independently ahalogen, and further Cl or F, and further F.

In another embodiment, the instant invention provides a catalyst systemcomprising procatalyst comprising a metal-ligand complex of Formula I,as described above and one or more co-catalysts.

When used to describe certain carbon atom-containing chemical groups(e.g., (C₁-C₄₀)alkyl), the parenthetical expression (C₁-C₄₀) can berepresented by the form “(C_(x)-C_(y)),” which means that theunsubstituted version of the chemical group comprises from a number xcarbon atoms to a number y carbon atoms, wherein each x and yindependently is an integer as described for the chemical group.

The term “substituted,” as used herein, with respect to a chemicalcompound, refers to a substituent that comprises at least one heteroatom(for example, O, S, N, P, etc.). Substituents include, but are notlimited to, the R^(S) substituents, as noted above, as the following: ahalogen atom, a polyfluoro substituent, a perfluoro substituent, F₃C—,FCH₂O—, F₂HCO—, F₃CO—, (R^(C))₃Si—, (R^(C))₃Ge—, (R^(C))O—, (R^(C))S—,(R^(C))S(O)—, (R^(C))S(O)₂—, (R^(C))₂P—, (R^(C))₂N—, (R^(C))₂C═N—, NC—,(R^(C))C(O)O—, (R^(C))OC(O)—, (R^(C))C(O)N(R^(C))—, and (R^(C))₂NC(O)—;wherein R^(C) is described above.

The term “unsubstituted,” as used herein, with respect to a chemicalcompound, refers to the lack of a substituent that comprises at leastone heteroatom (for example, O, S, N, P, etc.).

The term “hydrocarbyl,” as used herein, refers to a monovalent(monoradical or radical) chemical group containing only hydrogen andcarbon atoms.

The term “substituted hydrocarbyl,” as used herein, refers to ahydrocarbyl, in which at least one hydrogen atom is substituted with asubstituent that comprises at least one heteroatom.

The term “heterohydrocarbyl,” as used herein, refers to a hydocarbyl, inwhich at least one carbon atom, or CH group, or CH2 group, issubstituted with a heteroatom or a chemical group containing at leastone heteroatom. Heteroatoms include, but are not limited to, O, N, P andS.

The term “substituted heterohydrocarbyl,” as used herein, refers to aheterohydrocarbyl in which at least one hydrogen atom is substitutedwith a substituent that comprises at least one heteroatom.

The term “hydrocarbylene,” as used herein, refers to a divalent(diradical) chemical group containing only hydrogen and carbon atoms.

The term “substituted hydrocarbylene,” as used herein, refers to ahydrocarbylene, in which at least one hydrogen atom is substituted witha substituent that comprises at least one heteroatom.

The term “heterohydrocarbylene,” as used herein, refers to ahydrocarbylene, in which at least one carbon atom, or CH group, or CH2group, is substituted with a heteroatom or a chemical group containingat least one heteroatom. Heteroatoms include, but are not limited to, O,N, P and S.

The term “substituted heterohydrocarbylene,” as used herein, refers to aheterohydro-carbylene, in which at least one hydrogen atom issubstituted with a substituent that comprises at least one heteroatom.

In some embodiments, each of the chemical groups (e.g., X, L, R¹ throughR²², etc.) of the metal-ligand complex of Formula (I) may beunsubstituted (for example, without use of a substituent R^(S)). Inother embodiments, at least one of the chemical groups of themetal-ligand complex of Formula (I) independently contain one or more ofthe substituents (for example, R^(S)). Preferably, accounting for allchemical groups, there are not more than a total of 20 R^(S), morepreferably not more than a total of 10 R^(S), and still more preferablynot more than a total of 5 R^(S) in the metal-ligand complex of Formula(I). Where the invention compound contains two or more substituentsR^(S), each R^(S) independently is bonded to a same or different atom.

As used herein, the term “(C₁-C₄₀)hydrocarbyl” refers to hydrocarbonradical of from 1 to 40 carbon atoms. Each hydrocarbon radicalindependently may be aromatic (6 carbon atoms or more) or non-aromatic,saturated or unsaturated, straight chain or branched chain, cyclic(including mono- and poly-cyclic, fused and non-fused polycyclic,including bicyclic or acyclic, or a combination of two or more thereof;and each hydrocarbon radical independently is the same as, or differentfrom, another hydrocarbon radical, respectively. Each hydrocarbonradical may be optionally substituted with one or more R^(S)substituents, as defined above. A “(C₁-C₃₀)hydrocarbyl” is similarlydefined, as discussed above for the “(C₁-C₄₀)hydrocarbyl.”

Preferably, a (C₁-C₄₀)hydrocarbyl is independently a (C₁-C₄₀)alkyl, or a(C₃-C₄₀)cycloalkyl. More preferably, each of the aforementioned(C₁-C₄₀)hydrocarbyl groups independently has a maximum of 20 carbonatoms (i.e., (C₁-C₂₀)hydrocarbyl), and still more preferably a maximumof 12 carbon atoms. Further, the (C₁-C₄₀)hydrocarbyl is optionallysubstituted with one or more R^(S) substituents, as defined above.

As used herein, the term “(C₁-C₄₀)hydrocarbylene” refers to ahydrocarbon diradical of from 1 to 40 carbon atoms. Each hydrocarbondiradical independently may be aromatic (6 carbon atoms or more) ornon-aromatic, saturated or unsaturated, straight chain or branchedchain, cyclic (including mono- and poly-cyclic, fused and non-fusedpolycyclic, including bicyclic or acyclic, or a combination of two ormore thereof; and each hydrocarbon diradical independently is the sameas, or different from, another hydrocarbon diradical, respectively.Further the hydrocarbon radical may be optionally substituted with oneor more R^(S) substituents, as defined above.

Preferably, a (C₁-C₄₀)hydrocarbylene independently is a(C₃-C₂₀)cycloalkyl-(C₁-C₂₀)alkylene, (C₆-C₄₀)aryl, or(C₆-C₂₀)aryl-(C₁-C₂₀)alkylene. More preferably, each of theaforementioned (C₁-C₄₀)hydrocarbylene groups independently has a maximumof 20 carbon atoms (i.e., (C₁-C₂₀)hydrocarbyl), and still morepreferably a maximum of 12 carbon atoms. The (C₁-C₄₀)hydrocarbylene maybe optionally substituted with one or more R^(S) substituents, asdefined above.

The term “(C₁-C₄₀)heterohydrocarbyl” refers to a heterohydrocarbonradical of from 1 to 40 carbon atoms. Each heterohydrocarbonindependently may comprise one or more heteroatoms O; S; S(O); S(O)₂;Si(R^(C))₂; Ge(R^(C))₂; P(R^(P)); and N(R^(N)), wherein independentlyeach R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl, each R^(P) isunsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted(C₁-C₁₈)hydrocarbyl. Each (C₁-C₄₀)heterohydrocarbyl independently may besaturated or unsaturated, straight chain or branched chain, cyclic(including mono- and poly-cyclic, fused and non-fused polycyclic) oracyclic, or a combination of two or more thereof; and each isrespectively the same as or different from another. A“(C₁-C₃₀)heterohydrocarbyl” is similarly defined, as discussed above forthe “(C₁-C₄₀)heterohydro-carbyl.”

The term “(C₁-C₄₀)heterohydrocarbylene refers to a heterohydrocarbondiradical of from 1 to 40 carbon atoms. Each heterohydrocarbonindependently may comprise one or more heteroatoms O; S; S(O); S(O)₂;Si(R^(C))₂; Ge(R^(C))₂; P(R^(P)); and N(R^(N)), wherein independentlyeach R^(C) is unsubstituted (C₁-C₁₈)hydrocarbyl, each R^(P) isunsubstituted (C₁-C₁₈)hydrocarbyl; and each R^(N) is unsubstituted(C₁-C₁₈). Each (C₁-C₄₀)heterohydrocarbylene independently isunsubstituted or substituted (for example, by one or more R^(S)),aromatic or non-aromatic, saturated or unsaturated, straight chain orbranched chain, cyclic (including mono- and poly-cyclic, fused andnon-fused polycyclic) or acyclic, or a combination of two or morethereof; and each is respectively the same as or different from another.

Preferably, the (C₁-C₄₀)heterohydrocarbyl independently is(C₁-C₄₀)heteroalkyl, (C₁-C₄₀)hydrocarbyl-O—, (C₁-C₄₀)hydrocarbyl-S—,(C₁-C₄₀)hydrocarbyl-S(O)—, (C₁-C₄₀)hydrocarbyl-S(O)₂—,(C₁-C₄₀)hydrocarbyl-Si(R^(C))₂—, (C₁-C₄₀)hydrocarbyl-Ge(R^(C))₂—,(C₁-C₄₀)hydrocarbyl-N(R^(N))—, (C₁-C₄₀)hydrocarbyl-P(R^(P))—,(C₂-C₄₀)heterocycloalkyl.

Preferably, the (C₁-C₄₀)heterohydrocarbylene independently is(C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)alkylene,(C₃-C₂₀)cycloalkyl-(C₁-C₁₉)heteroalkylene,(C₂-C₁₉)heterocycloalkyl-(C₁-C₂₀)heteroalkylene, (C₁-C₄₀)heteroaryl,(C₁-C₁₉)heteroaryl-(C₁-C₂₀)alkylene,(C₆-C₂₀)aryl-(C₁-C₁₉)heteroalkylene, or(C₁-C₁₉)heteroaryl-(C₁-C₂₀)heteroalkylene.

The term “halogen atom” means fluorine atom (F), chlorine atom (Cl),bromine atom (Br), or iodine atom (I) radical. Preferably each halogenatom independently is the Br, F, or Cl radical, and more preferably theF or Cl radical. The term “halide” means fluoride (P), chloride (Cr),bromide (Br⁻), or iodide (I⁻) anion.

Preferably, there are no O—O, S—S, or O—S bonds, other than O—S bonds inan S(O) or S(O)₂ diradical functional group, in the metal-ligand complexof Formula (I). More preferably, there are no O—, N—N, P—P, N—P, S—S, orO—S bonds, other than O—S bonds in an S(O) or S(O)₂ diradical functionalgroup, in the metal-ligand complex of Formula (I).

The term “saturated” means lacking carbon-carbon double bonds,carbon-carbon triple bonds, and (in heteroatom-containing groups)carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds.

The term “unsaturated” means containing one or more carbon-carbon doublebonds, carbon-carbon triple bonds, and (in heteroatom-containing groups)carbon-nitrogen, carbon-phosphorous, and/or carbon-silicon double bonds.

M is titanium, zirconium, or hafnium. In one embodiment, M is zirconiumor hafnium, and in another embodiment M is hafnium. In anotherembodiment, M is zirconium. In some embodiments, M is in a formaloxidation state of +2, +3, or +4. In some embodiments, n is 0, 1, 2, or3. Each X independently is a monodentate ligand that is neutral,monoanionic, or dianionic; or two Xs are taken together to form abidentate ligand that is neutral, monoanionic, or dianionic. X and n arechosen in such a way that the metal-ligand complex of Formula (I) is,overall, neutral. In some embodiments each X independently is themonodentate ligand. In one embodiment, when there are two or more Xmonodentate ligands, each X is the same. In some embodiments themonodentate ligand is the monoanionic ligand. The monoanionic ligand hasa net formal oxidation state of −1. Each monoanionic ligand mayindependently be hydride, (C₁-C₄₀)hydrocarbyl carbanion,(C₁-C₄₀)heterohydrocarbyl carbanion, halide, nitrate, HC(O)O⁻,(C₁-C₄₀)hydrocarbylC(O)O⁻, HC(O)N(H)⁻, (C₁-C₄₀)hydrocarbyl-C(O)N(H)⁻,(C₁-C₄₀)hydrocarbylC(O)N((C₁-C₂₀)hydrocarbyl)⁻, R^(K)R^(L)B⁻,R^(K)R^(L)N⁻, R^(K)O⁻, R^(K)S⁻, R^(K)R^(L)P⁻, or R^(M)R^(K)R^(L)Si⁻,wherein each R^(K), R^(L), and R^(M) independently is hydrogen,(C₁-C₄₀)hydrocarbyl, or (C₁-C₄₀)heterohydrocarbyl, or R^(K) and R^(L)are taken together to form a (C₂-C₄₀)hydrocarbylene or(C₁-C₄₀)heterohydrocarbylene and R^(M) is as defined above.

In some embodiments, at least one monodentate ligand of X independentlyis the neutral ligand. In one embodiment, the neutral ligand is aneutral Lewis base group that is R^(X)NR^(K)R^(L), R^(K)OR^(L),R^(K)SR^(L), or R^(X)PR^(K)R^(L), wherein each R^(X) independently ishydrogen, (C₁-C₄₀)hydrocarbyl, [(C₁-C₁₀)hydrocarbyl]₃Si,[(C₁-C₁₀)hydrocarbyl]₃Si(C₁-C₁₀)hydro-carbyl, or(C₁-C₄₀)heterohydrocarbyl and each R^(K) and R^(L) independently is asdefined above.

In some embodiments, each X is a monodentate ligand that independentlyis a halogen atom, unsubstituted (C₁-C₂₀)hydrocarbyl, unsubstituted(C₁-C₂₀)hydrocarbylC(O)O—, or R^(K)R^(L)N— wherein each of R^(K) andR^(L) independently is an unsubstituted (C₁-C₂₀)hydrocarbyl. In someembodiments each monodentate ligand X is a chlorine atom,(C₁-C₁₀)hydrocarbyl (e.g., (C₁-C₆)alkyl or benzyl), unsubstituted(C₁-C₁₀)hydrocarbylC(O)O—, or R^(K)R^(L)N— wherein each of R^(K) andR^(L) independently is an unsubstituted (C₁-C₁₀)hydrocarbyl.

In some embodiments, there are at least two X and the two X are takentogether to form the bidentate ligand. In some embodiments the bidentateligand is a neutral bidentate ligand. In one embodiment, the neutralbidentate ligand is a diene of formula(R^(D))₂C═C(R^(D))—C(R^(D))═C(R^(D))₂, wherein each R^(D) independentlyis H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. In someembodiments the bidentate ligand is a monoanionic-mono(Lewis base)ligand. The monoanionic-mono(Lewis base) ligand may be a 1,3-dionate offormula (D): R^(E)—C(O^(—))═CH—C(═O)—R^(E)(D), wherein each R^(D)independently is H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. Insome embodiments the bidentate ligand is a dianionic ligand. Thedianionic ligand has a net formal oxidation state of −2. In oneembodiment, each dianionic ligand independently is carbonate, oxalate(i.e., ⁻O₂CC(O)O⁻), (C₂-C₄₀)hydrocarbylene dicarbanion,(C₁-C₄₀)hetero-hydrocarbylene dicarbanion, or sulfate.

As previously mentioned, number and charge (neutral, monoanionic,dianionic) of X are selected depending on the formal oxidation state ofM such that the metal-ligand complex of Formula (I) is, overall,neutral.

In some embodiments, each X is the same, wherein each X is methyl;ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl;trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments nis 2 and each X is the same.

In some embodiments, at least two X are different. In some embodiments,n is 2 and each X is a different one of methyl; ethyl; 1-propyl;2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl;benzyl; and chloro.

The integer n indicates number of X. In one embodiment, n is 2 or 3, andat least two X independently are monoanionic monodentate ligands, and athird X, if present, is a neutral monodentate ligand. In someembodiments n is 2, at two X are taken together to form a bidentateligand. In some embodiments, the bidentate ligand is2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.

In some embodiments, each Z independently is O, S,—N[(C₁-C₄₀)hydrocarbyl]—, or —P[(C₁-C₄₀)hydrocarbyl]—. In someembodiments, each Z is different. In some embodiments, one Z is O, andone Z is —N(CH₃)—. In some embodiments, one Z is O, and one Z is S. Insome embodiments, one Z is S, and one Z is —N[(C₁-C₄₀)hydrocarbyl]-(e.g., —N(CH₃)—). In some embodiments, each Z is the same. In someembodiments, each Z is O. In some embodiments, each Z is S. In someembodiments, each Z is —N[(C₁-C₄₀)hydrocarbyl]- (e.g., —N(CH₃)—). Insome embodiments, at least one, and in some embodiments each Z is—P[(C₁-C₄₀)hydrocarbyl]- (e.g., —P(CH₃)—).

In some embodiments, L is selected from the following: —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—; —CH(CH₃)CH₂CH(CH₃)—; —CH(CH₃)CH(CH₃)CH(CH₃)—;—CH₂C(CH₃)₂CH₂—; 1,3-cyclopentane-diyl; or 1,3-cyclohexane-diyl. In someembodiments L comprises the 4-carbon atom linker backbone (e.g., L is—CH₂CH₂CH₂CH₂—; —CH₂C(CH₃)₂C(CH₃)₂CH₂—; 1,2-bis(methylene)cyclohexane;or 2,3-bis(methylene)-bicycico[2.2.2]octane). In some embodiments, Lcomprises the 5-carbon atom linker backbone (e.g., L is—CH₂CH₂CH₂CH₂CH₂— or 1,3-bis(methylene)cyclohexane). In someembodiments, L comprises the 6-carbon atom linker backbone (e.g., L is—CH₂CH₂CH₂CH₂CH₂CH₂— or 1,2-bis(ethylene)cyclohexane).

Process for Producing Procatalyst

In some embodiments, the ligands of the invention may be prepared usingknown procedures. Specifically, the ligands of the invention may beprepared using a variety of synthetic routes, depending on the variationdesired in the ligand. In general, building blocks are prepared that arethen linked together with a bridging group. Variations in the R groupsubstituents can be introduced in the synthesis of the building blocks.

Variations in the bridge can be introduced with the synthesis of thebridging group. Specific ligands within the scope of this invention maybe prepared according to the general schemes shown below, where buildingblocks are first prepared, and then coupled together. There are severaldifferent ways to use these building blocks. In one embodiment,generally, each of the optionally substituted phenyl rings is preparedas a separate building block. The desired optionally substituted phenylsare then combined into bi-phenyl building blocks, which are then bridgedtogether. In another embodiment, the optionally substituted phenylbuilding blocks are bridged together, and then additional, optionallysubstituted phenyl building blocks are added to form the bridged bi-arylstructures. The starting materials or reagents used are generallycommercially available, or are prepared via routine synthetic means.

In the schemes below, the term ligand refers to the organic precursor tothe pro-catalyst. The pro-catalyst is derived from a reaction of theligand with a suitable metallic (titanium, zirconium, or hafnium)precursor. Common abbreviations are listed in the key system are asfollows: LG: generic leaving group; PG: generic protecting group, commonexamples include:

R, L, M, Z, X: as defined above; Ha: halide, most commonly Br or I; Me:methyl; Et: ethyl; Ph: phenyl; i-Pr: iso-propyl; t-Bu: tert-butyl;t-Oct: tert-octyl; Ts: toluene sulfonate; THF: tetrahydrofuran; Et₂O:diethyl ether; DMF: dimethylformamide; EtOAc: ethyl acetate; DIAD:diisopropyl azodicarboxylate; GC: gas chromatography; LC: liquidchromatography; TLC: thin layer chromatography; NMR: nuclear magneticresonance; PTSA: para-toluene sulfonic acid; NIS: N-iodosuccinimide1a. Preparation of 2-Substituted Protected Phenols (Protocol 1,Carbon-Nitrogen Coupling).

A three-neck, round-bottomed flask, in a glove box, is charged with thedesired protected phenol (approximately 1.0 equivalents), the desiredaryl-nitrogen compound or nitrogen heterocyclic (approximately 0.6equivalents), K₃PO₄ (approximately 2.1 equivalents), anhydrous CuI(approximately 0.03 equivalents), dried toluene (approximately 2 mL permmol of phenol), and an appropriate N,N′-disubstituted diamine(approximately 0.08 equivalents). The reaction mixture is then heatedunder reflux. The reaction progress can be monitored by a suitabletechnique (e.g. GC/MS, NMR spectroscopy, TLC), and, in some cases,additional anhydrous CuI (approximately 0.03 equivalents) andN,N-disubstituted diamine (approximately 0.08 equivalents) is added tothe mixture, and heating under reflux continued, until such a time, whenthe conversion is observed to be complete. The reaction is then allowedto cool to room temperature, and filtered through a small silica plug,washed with THF, and concentrated, to give the crude product. This crudematerial can be purified by either recrystallization or flashchromatography on silica gel.

1b. Preparation of 2-Substituted Protected Phenols (Protocol 2,Carbon-Carbon Coupling).

A three-neck, round-bottomed flask, placed under a nitrogen atmosphere,is charged with approximately equimolar quantities of the aryl halideand the borylated aryl compound, NaOH (approximately 6 equivalentsrelative to aryl halide), Pd(PPh₃)₄ (approximately 0.02 equivalentsrelative to aryl halide), degassed toluene (approximately 5 mL per mmolof aryl halide), and degassed water (approximately 1 mL per mmol of arylhalide). The system is nitrogen-sparged, and the contents are thenheated to 110° C. for approximately 24 hours. The reaction is cooled,and the volatiles removed under vacuum. The residue is taken up in Et₂O,washed with brine, dried over anhydrous magnesium sulfate, filteredthrough a pad of silica gel, and then concentrated. This crude materialcan be purified by either recrystallization or flash chromatography onsilica gel.

2. Preparation of Borylated 2-Substituted Protected Phenols:

To an oven dried, three-neck, round-bottomed flask, under nitrogenatmosphere, is added the desired protected phenol (approximately 1.0equivalents) and dry THF (approximately 6 mL per mmol of protectedphenol). This solution was cooled to approximately 0-10° C. (ice-waterbath), and 2.5 M n-butyl lithium in hexanes (approximately 2.2equivalents) is added slowly. After stirring for approximately 4 hours,the desired boronic ester or boronic acid (approximately 2.2equivalents) is added slowly. The mixture is stirred for one hour atapproximately 0-10° C., before allowing the reaction to warm to roomtemperature, and then stirred for approximately 18 hours. To thereaction mixture is added cold, saturated aqueous sodium bicarbonate(approximately 6 mL per mmol of protected phenol). The mixture isextracted with several portions of methylene chloride. The organicphases are combined, and washed with cold saturated aqueous sodiumbicarbonate, brine, then dried over anhydrous magnesium sulfate,filtered, and concentrated to give the crude product. Purification canbe accomplished by recrystallization from a suitable solvent (e.g.,acetonitrile, toluene, hexane, or methanol).

3a. Preparation of Symmetrical Bridging Fragments.

Mitsonobu-type: An oven, dried three-neck, round-bottomed flask,equipped with an addition funnel, is placed under nitrogen atmosphere,and charged with the desired aryl halide (approximately 1.0equivalents), the desired connecting unit (containing the L moiety andthe R¹⁷-R²² groups, approximately 0.45 equivalents), triphenylphosphine(approximately 1.0 equivalents), and THF (approximately 1.0 mL per mmolof aryl halide). The addition funnel is then charged with DIAD(approximately 1.0 equivalents) and THF (approximately 0.5 mL per mmolof aryl halide). The contents in the flask are cooled to approximately2-5° C., in an ice-water bath, and the DIAD solution in the additionfunnel is added, at such a rate, to maintain the reaction temperature at2-5° C. The resulting mixture is stirred at 2-5° C. for an additionalone hour, subsequent to the DIAD addition, then allowed to warm up toambient temperature, and stirred overnight. The volatiles are removedunder vacuum, and the resulting residue is extracted with alkanesolvent, and sequentially washed with 1M NaOH, water, 1N HCl, and water.The organic portion is collected, and dried under vacuum. Purificationcan be accomplished by recrystallization from a suitable solvent (e.g.acetonitrile, toluene, hexane, or methanol), or column chromatography onsilica gel.

S_(N)2-type: To a solution of the desired aryl halide (approximately 1.0equivalents) and desired connecting unit (containing the L moiety andthe R¹⁷-R²² groups, approximately 0.45 equivalents), in acetone(approximately 7.0 mL per mmol of aryl halide), is added K₂CO₃(approximately 2.5 equivalents). The reaction mixture is then heatedunder reflux for approximately 36 hours. The resulting suspension isthen cooled, filtered, and concentrated under vacuum. Purification canbe accomplished by recrystallization from a suitable solvent (e.g.acetonitrile, toluene, hexane, or methanol), or column chromatography onsilica gel.

3b. Preparation of Unsymmetrical Bridging Fragments.

To a solution of the desired aryl halide (approximately 1.0 equivalents)and desired connecting unit (containing the L moiety and the R¹⁷-R²²groups, approximately 1.5 equivalents), in acetone (approximately 7.0 mLper mmol of aryl halide,) is added K₂CO₃ (approximately 2.5equivalents). The reaction mixture is then heated under reflux forapproximately 36 hours. The resulting suspension is then cooled,filtered, and concentrated under vacuum. Purification can beaccomplished at this stage by recrystallization from a suitable solvent(e.g. acetonitrile, toluene, hexane, or methanol), or columnchromatography on silica gel. The obtained material is then subjected toan analogous sequential reaction, by combining it with another arylhalide (approximately 1.0 equivalents), and K₂CO₃ (approximately 2.5equivalents), in acetone (approximately 7.0 mL per mmol of aryl halide),and heating under reflux. The resulting suspension is then cooled,filtered, and concentrated under vacuum. Purification can beaccomplished recrystallization from a suitable solvent (e.g.acetonitrile, toluene, hexane, or methanol), or column chromatography onsilica gel.

5a. Preparation of Ligand (Simultaneous Double Suzuki Reaction).

To an oven dried, three-neck, round-bottomed flask, under nitrogenatmosphere, is added the bis-arylhalide (approximately 1.0 equivalents)and the borylated protected phenol (approximately 2.2 equivalents)dissolved in toluene (approximately 5 mL per mmol of bis-arylhalide),under a nitrogen atmosphere with stirring. To this, is added, NaOH(approximately 1.0 equivalents) dissolved in water, (approximately 10 mLper mmol of NaOH), followed by quick addition of Pd(PPh₃)₄(approximately 0.04 equivalents), and the reaction heated to 88° C. Thecourse of the reaction can be monitored via LC. When deemed complete,the reaction vessel is cooled to ambient temperature, and the stirringhalted. The caustic layer is removed from the resulting bisphasicmixture, and a 20% aqueous HCl solution is added (approximately 1.5 mLper mmol of bis-arylhalide) to the remaining organic portion. Theresulting mixture is heated under reflux for approximately 8 hours. Thereactor is cooled to ambient temperature, the aqueous layer removed, andthe organic layer washed with brine, and then dried over MgSO₄. Thismixture is filtered, and concentrated, to provide the crude product,which can be purified by recrystallization from a suitable solvent (e.g.acetonitrile, toluene, hexane, or methanol), or column chromatography onsilica gel.

5b. Preparation of Ligand (Sequential Suzuki Reactions).

To an oven dried, three-neck, round-bottomed flask, under nitrogenatmosphere, is added the bis-arylhalide (approximately 1.0 equivalents)and the borylated protected phenol (approximately 1.0 equivalents)dissolved in toluene (approximately 5 mL per mmol of bis-arylhalide),under a nitrogen atmosphere with stirring. To this is added, NaOH(approximately 1.0 equivalents) dissolved in water, (approximately 10 mLper mmol of NaOH), followed by quick addition of a suitable palladiumcatalyst (approximately 0.04 equivalents), and the reaction is heated to88° C. The course of the reaction can be monitored via LC. When deemedcomplete, the reaction vessel is cooled to ambient temperature, and thesecond borylated protected phenol (approximately 1.0 equivalents), and asuitable palladium catalyst (approximately 0.04 equivalents). Thereaction is heated to 88° C., and the course of the reaction can beagain be monitored via LC. When deemed complete, the reaction vessel iscooled to ambient temperature, and the stirring halted. The causticlayer is removed from the resulting bisphasic mixture, and a 20% aqueousHCl solution is added (approximately 1.5 mL per mmol of bis-arylhalide)to the remaining organic portion. The resulting mixture is heated underreflux for approximately 8 hours. The reactor is cooled to ambienttemperature, the aqueous layer removed, and the organic layer washedwith brine, and then dried over MgSO₄. This mixture is filtered, andconcentrated, to provide the crude product, which can be purified byrecrystallization from a suitable solvent (e.g. acetonitrile, toluene,hexane, or methanol), or column chromatography on silica gel.

7. Preparation of Pro-Catalyst.

An oven, dried three-neck, round-bottomed flask, under nitrogenatmosphere, is charged with MCl₄ (approximately 1.0 equivalents) andcold toluene or hexane (approximately 10 mL per mmol of ligand, at −40to −20° C. XMgBr (approximately 4.0 equivalents) is then added to thecold suspension, and the resulting mixture is stirred for 2-15 minutes.The ligand (approximately 0.95 equivalents) is then added, and thereaction mixture is allowed to warm to ambient temperature, and stirredfor approximately 4 hours, and then dried under vacuum. The resultingresidue is extracted with hexane and/or toluene, filtered, and driedunder vacuum. This crude material can be further purified byrecrystallization from a suitable solvent (e.g. hexane, toluene).

EXPERIMENTAL

The following examples illustrate the present invention but are notintended to limit the scope of the invention.

Specific Embodiments for Synthesis of Inventive Catalyst EXAMPLE 1 1a.Preparation of Ligand I (L1)

A round bottom flask was charged with3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole(7.285 g, 11.91 mmol) andmeso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methylbenzene) (2.194g, 4.96 mmol), and 60 mL of THF. Na₂CO₃ (3.156 g, 29.78 mmol) wasdissolved in 30 mL of water, and added to the THF solution, forming abiphasic solution, which was then sparged with N₂ for 15 minutes.Pd(P(t-Bu)₃)₂ (0.076 g, 0.15 mmol) was dissolved in 20 mL degassed THF,in a nitrogen-filled glovebox, then added to the reaction mixture, whichwas heated under reflux, under nitrogen for 24 hours. The reactionmixture was allowed to cool to ambient temperature, and then the aqueousphase was separated and discarded. THF was removed from the organicphase on a rotary evaporator, and dichloromethane (120 mL) was added tothe residue, and the solution was washed with 120 mL of water. Brine (30mL) was added to aid phase separation.

The organic phase was collected and evaporated to dryness under vacuum.The residue was dissolved in 50 mL of diethyl ether, filtered through aplug of silica gel and evaporated to dryness under reduced pressure.MeOH (100 mL), THF (40 mL) and concentrated HCl (4 drops) were added tothe residue, and the solution was refluxed for two hours. The reactionmixture was allowed cool to room temperature, but no precipitationoccurred. Therefore, the solution was concentrated to approximately halfits original volume on a rotary evaporator, causing orange-coloredsolids to form. The solids were filtered, washed with methanol and driedunder vacuum (1.83 g). The mother liquor was evaporated to dryness, thenthe residue was dissolved in diethyl ether (approximately 15 mL), andpoured into approximately 200 mL of methanol, causing a small amount ofprecipitate to form. The volume was decreased by half on under vacuum,causing more solids to crash out. The pale orange solids were filtered,washed with methanol and dried under vacuum, to give pure product (1.90g). A third crop of product (0.26 g) was recovered from the motherliquor. Overall isolated yield: 3.99 g, 64%. ¹H NMR (400 MHz, CDCl₃) δ8.16 (t, J=2.1 Hz, 4H), 7.40 (m, 8H), 7.17 (d, J=2.2 Hz, 2H), 7.11 (t,J=8.1 Hz, 4H), 6.88 (dd, J=8.4, 2.2 Hz, 2H), 6.64 (d, J=8.3 Hz, 2H),6.22 (s, 2H), 4.43 (m, 2H), 2.31 (s, 6H), 2.09 (dt, J=13.8, 6.8 Hz, 1H),1.75 (s, 4H), 1.64 (dt, J=16.1, 5.9 Hz, 1H), 1.47 (s, 18H), 1.45 (s,18H), 1.39 (s, 12H), 1.08 (d, J=6.0 Hz, 6H), and 0.82 (s, 18H).

1b. Preparation of Pro-Catalyst I (I1).

The ligand (0.500 g, 0.40 mmol) was dissolved in 10 mL of hexane, undera dry nitrogen atmosphere, and the solution was added to a stirredsuspension of ZrCl₄ (0.093 g, 0.40 mmol) in 5 mL of hexane. MeMgBr (0.63mL, 1.64 mmol; 2.6 M in Et₂O) was added dropwise, via syringe, atambient temperature. The mixture was stirred for 14 hours. The color ofthe reaction mixture slowly turned black. The suspension was filtered,and the filtrate evaporated to dryness under vacuum. Hexane (10 mL) wasadded to the residue, the light suspension was filtered, and thefiltrate evaporated to dryness under vacuum. The treatment with hexanewas repeated, and the product was thoroughly dried under vacuum, toafford I1 in good purity as a tan solid (0.193 g, 35%). ¹H NMR (400 MHz,C₆D₆): δ 8.69 (t, J=2.0 Hz, 2H), 8.45 (d, J=1.7 Hz, 1H), 8.40 (d, J=1.7Hz, 1H), 7.38-7.85 (m, 16H), 7.13 (d, J=2.2 Hz, 1H), 7.08 (d, J=2.3 Hz,1H), 6.65 (dd, J=8.4, 2.1 Hz, 1H), 6.62 (dd, J=8.3, 2.1 Hz, 1H), 5.02(d, J=6.5 Hz, 1H), 4.85 (d, J=6.8 Hz, 1H), 4.33 (dt, J=13.2, 6.8 Hz,1H), 3.86 (m, 1H), 1.88 (s, 3H), 1.87 (s 3H), 0.79-1.71 (m, 70H), 0.73(d, J=6.7 Hz, 3H), 0.54 (d, J=6.7 Hz, 3H), −0.70 (s, 3H), and −0.86 (s,3H). ¹³C{¹H} NMR (101 MHz, CDCl₃) δ 151.4, 147.9, 142.5, 142.2, 139.8,139.7, 132.7, 131.7, 129.9, 129.0, 128.8, 127.8, 126.6, 125.0, 123.4,123.2, 116.2, 115.5, 109.5, 73.4, 57.1, 42.4, 38.2, 34.7, 32.4, 32.1,32.1, 31.9, 31.7, 31.6, 20.6, and 19.7.

EXAMPLE 2 2a. Preparation ofmeso-4,4′-pentane-2,4-diylbis(oxy)bis(1-(tert-butyl)-3-iodobenzene)

A round-bottom flask was charged with meso-ditosylate (3.1 g, 7.5 mmol),2-iodo-4-t-octylphenol (5.0 g, 15.1 mmol), and DMF (100 mL). K₂CO₃ (4.2g, 30.1 mmol) was added, and the reaction was heated under reflux forone day. The volatiles were then removed by bulb to bulb distillation,yielding a brown solid. The solid was taken up in Et₂O (250 mL), rinsedwith 3M NaOH solution (2×100 mL), brine (100 mL), and then dried overMgSO₄. The reaction mixture was filtered, and concentrated on a rotaryevaporator, to yield the crude product, and was further purified bycolumn chromatography (SiO₂, hexanes/EtOAc 95:5) to afford the desiredproduct (1.6 g, 29% theoretical 5.5 g). ¹H NMR (400 MHz, CDCl₃) δ 7.74(d, J=2.3 Hz, 2H), 7.28 (dd, J=8.7, 2.3 Hz, 1H), 6.87 (d, J=8.7 Hz, 2H),4.77-4.61 (m, 2H), 2.42 (dt, J=13.8, 6.8 Hz, 1H), 1.84 (dt, J=14.0, 5.9Hz, 1H), 1.68 (s, 4H), 1.36 (d, J=6.1 Hz, 6H), 1.33 (s, 12H), 0.74 (s,18H).

2d. Preparation of Ligand 2 (L2).

A round bottom flask was charged withmeso-4,4′-pentane-2,4-diylbis(oxy))bis(1-(tert-octyl)-3-iodobenzene))(0.790 g, 1.08 mmol) and9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole(1.052 g, 2.37 mmol), and 40 mL of THF. Na₂CO₃ (0.686 g, 6.47 mmol) wasdissolved in 20 mL of water, and added to the THF solution, forming abiphasic solution, which was then sparged with N₂ for 15 minutes.Pd(P(t-Bu)₃)₂ (0.017 g, 0.03 mmol) was dissolved in 6 mL degassed THF inthe drybox, and then added to the reaction mixture, which was heatedunder reflux, under nitrogen for three days. After allowing the reactionmixture to cool to ambient temperature, the aqueous phase was discarded,and THF was removed from the organic phase using a rotary evaporator.Dichloromethane (80 mL) was added, and the solution was washed with 80mL of water mixed with 20 mL of brine. The organic phase was evaporatedto dryness, under vacuum, and the residue was dissolved in 50 mL diethylether, filtered through a plug of silica gel, and evaporated to drynessunder vacuum. Methanol (80 mL), THF (15 mL) and conc. HCl (6 drops) wereadded, and the solution was refluxed overnight, and then the solvent wasremoved, under vacuum, and the residue was triturated with a smallamount of methanol, and again dried under vacuum. The resulting materialwas purified via column chromatography on silica gel, gradient elutingwith 1% EtOAc in hexane→5% EtOAc in hexane, furnishing the pure ligandL2 (0.820 g, 74%). ¹H NMR (400 MHz, CDCl₃): δ 8.15 (dd, J=7.5, 1.2 Hz,4H), 7.40 (d, J=2.5 Hz, 2H), 7.33 (m, 10H), 7.23 (m, 6H), 7.16 (dd,J=8.5, 2.3 Hz, 2H), 6.66 (d, J=8.7 Hz, 2H), 6.23 (s, 2H), 4.52 (m, 2H),2.47 (s, 6H), 2.22 (m, 1H), 1.74 (s, 4H), 1.71 (m, 1H), 1.38 (d, J=6.1Hz, 12H), 1.18 (d, J=6.0 Hz, 6H), and 0.75 (s, 18H). ¹³C{¹H} NMR (101MHz, CDCl₃) δ 151.1, 148.3, 144.0, 141.3, 141.2, 131.7, 130.3, 130.3,129.2, 129.1, 127.19, 126.8, 125.6, 125.6, 125.2, 123.3, 123.2, 120.2,120.6, 119.5, 113.8, 110.3, 110.2, 72.7, 57.0, 42.7, 38.1, 32.4, 31.8,31.5, 20.7, and 19.8.

2d. Preparation of Pro-Catalyst 2 (12).

The ligand L4 (0.500 g, 0.49 mmol) was dissolved in 10 mL of toluene,under a dry nitrogen atmosphere, and the solution was added to a stirredsuspension of ZrCl₄ (0.114 g, 0.490 mmol) in 5 mL of toluene. MeMgBr(0.77 mL, 2.00 mmol; 2.6 M in Et₂O) was added dropwise via syringe atambient temperature. The mixture was stirred for two hours. The color ofthe reaction mixture slowly turned black. Hexane (5 mL) was added to thesuspension, which was then filtered, and the filtrate evaporated todryness under vacuum. Toluene (15 mL) and hexane (5 mL) were added tothe residue, the light suspension was filtered, and the filtrateevaporated to dryness under vacuum, furnishing 14 in high purity (292mg, 52%). ¹H NMR (400 MHz, C₆D₆) δ 8.35 (m, 2H), 8.10 (m, 2H), 7.67 (m,1H), 7.57-7.32 (m, 12H), 7.23-7.08 (m, 5H), 6.84 (ddd, J=10.8, 8.5, 2.5Hz, 2H), 5.04 (d, J=8.5 Hz, 1H), 4.87 (d, J=8.6 Hz, 1H), 4.04 (m, 1H),3.68 (m, 1H), 2.22 (s, 6H), 1.76-1.60 (m, 4H), 1.24 (s, 3H), 1.22 (s,3H), 1.21 (s, 3H), 1.19 (s, 3H), 0.76 (s, 9H), 0.75 (s, 9H), 0.50 (d,J=6.2 Hz, 3H), 0.32 (d, J=6.5 Hz, 3H), −0.77 (s, 3H), and −0.91 (s, 3H).

EXAMPLE 3 3a. Preparation of 3,6-bis(1,1-dimethylethyl)-9H-carbazole

A 500 mL, three-neck, round bottom flask, equipped with an overheadstirrer, nitrogen gas bubbler, and an addition funnel, was charged with20.02 g (120.8 mmol) of carbazole, 49.82 g (365.5 mmol) of ZnCl₂, and300 mL of nitromethane at room temperature. To the resulting dark brownslurry, was added, 49.82 g (365.5 mmol) of 2-chloro-2-methylpropane(also known as tertiary-butyl chloride), dropwise from the additionfunnel, over the period of 2.5 hours. After completing the addition, theresulting slurry was stirred for an additional 18 hours, and thereaction mixture was poured into 800 mL of ice cold water, and extractedwith methylene chloride (3×500 mL). The combined extracts were driedwith anhydrous magnesium sulfate, filtered, and concentrated, first byrotary evaporation, and then by evaporation under high vacuum to removenitromethane. The resulting residue was dissolved in hot methylenechloride (70 mL), followed by hot hexanes (50 mL), and the resultingsolution was cooled to room temperature, and then placed it in arefrigerator overnight. The resulting solids which formed were isolated,washed with cold hexanes, and then dried under high vacuum to yield10.80 g (32.0%) of the desired product as off-white crystals.

¹H NMR (400 MHz, CDCl₃) δ 8.11 (d, J=1.6 Hz, 2H), 7.75 (s, 1H), 7.48(dd, J=8.5, 1.9 Hz, 2H), 7.31 (d, J=8.5 Hz, 2H), 1.48 (s, 18H). ¹³C{¹H}NMR (101 MHz, CDCl₃) δ 142.17 (s), 137.96 (s), 123.45 (s), 123.28 (s),116.11 (s), 109.97 (s), 34.73 (s), 32.09 (s).

3b. Preparation of 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol

To a stirred solution of 10.30 g (50.00 mmol) of4-(2,4,4-trimethylpentan-2-yl)phenol, in 125 mL of methanol at 0° C.,was added 7.48 g (50.00 mmol) of NaI and 2.00 g (50.0 mmol) of NaOH. Tothe resulting mixture, was added, 86 mL of 5% aqueous NaOCl solution(commercial bleach) over a one hour period. The resulting slurry wasstirred for one more hour at 0° C., then 30 mL of aqueous 10% Na₂S₂O₃solution was added, and the resulting reaction mixture was acidifiedwith the addition of dilute hydrochloric acid. The resulting mixture wasextracted with methylene chloride, and the resulting organic layer waswashed with brine, and then dried over anhydrous magnesium sulfate. Thevolatiles were removed under vacuum, and the resulting residue waspurified by flash chromatography on silica gel, eluting with 5 volumepercent (vol %) ethyl acetate in hexanes to yield 11.00 g (66%) of thedesired product as a viscous oil. ¹H NMR (CDCl₃) δ 7.60 (d, J=2.5 Hz,1H), 7.25 (dd, J=8.5 and 2.2 Hz, 1H), 6.90 (d, J=8.5 Hz, 1H), 5.13 (s,1H), 1.69 (s, 2H), 1.32 (s, 6H) and 0.74 (s, 9H). ¹³C{¹H} NMR (CDCl₃) δ152.21, 144.52, 135.56, 128.03, 114.17, 85.36, 56.92, 38.01, 32.43,31.90 and 31.64. GC/MS (m/e): 332 (M⁺).

3c. Preparation of2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran

To a stirred solution of 4.91 g (14.8 mmol) of4-(2,4,4-trimethylpentan-2-yl)phenol and 1.50 g (17.8 mmol) of3,4-dihydropyran, in 5 mL of methylene chloride, at 0° C., was added,0.039g (0.205 mmol) of para-toluenesulfonic acid monohydrate. Theresulting solution was allowed to warm to room temperature, and stirredthereat for approximately 10 minutes. Then triethylamine (0.018 g, 0.178mmol) was added, and the resulting mixture was diluted with 50 mL ofmethylene chloride, and successively washed with 50 mL each of 1M NaOH,water, and brine. The organic phase was dried with anhydrous magnesiumsulfate, filtered, and concentrated, to give a crude material, which waspurified by flash chromatography on silica gel, using 5 vol % ethylacetate in hexanes, to yield 5.18 g (93.12%) of the desired product as agolden oil. ¹H NMR (CDCl₃) δ 7.74 (d, J=2.3 Hz, 1H), 7.27 (dd, J=2.3 and8.6 Hz, 1H), 6.99 (d, J=8.6 Hz, 1H), 5.49 (m, 1H), 3.91 (m, 1H), 3.61(m,1H), 2.20-1.60 (m, 6H), 1.69 (s, 2H), 1.34 (s, 6H) and 0.75 (s, 9H).¹³C[¹H] NMR (CDCl₃) δ 153.27, 145.49, 136.98, 127.08, 114.44, 96.72,87.09, 61.69, 56.91, 37.95, 32.33, 31.81, 31.52, 31.44, 30.26, 25.27,18.36.

3d. Preparation of3,6-di-tert-butyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5-(2,4,4-trimethyl-pentan-2-yl)phenyl)-9H-carbazole

To a 50 mL, three necked, round bottom flask, equipped with a stir barand condenser, under N₂ atmosphere, was added the following: 20 mL ofdry toluene, 5.00 g (12.01 mmol) of2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran;3.56 g (12.01 mmol) of 3,6-di-tert-butyl carbazole, 0.488 g (2.56 mmol)of CuI, 7.71 g (36.2 mmol) of K₃PO₄, and 0.338 g (3.84 mmol) ofN,N′-dimethylethylenediamine. The resulting reaction mixture was heated,under reflux, for 48 hours, cooled, and filtered through a bed of silicagel. The silica gel was rinsed with tetrahydrofuran (THF), and theresulting solution was concentrated to give a crude residue.Purification was accomplished by recrystallization from acetonitrile, toyield 4.57 g (67.0%) of the desired product as a white solid. ¹H NMR(CDCl₃) δ 8.13 (t, J=1.71 Hz, 1H), 7.48 (d, J=2.4 Hz, 1H), 7.40 (m, 3H),7.31 (d, J=8.68 Hz, 1H), 7.14 (d, J=8.68 Hz, 1H), 7.08 (d, J=8.56 Hz,1H), 5.22 (t, J=2.81 Hz, 1H), 3.72(td, J=11.12 and 2.8 Hz, 1H), 3.47(dt, J=11.12 and 3.47 Hz, 1H), 1.75 (s, 2H), 1.474 (s, 9H), 1.472 (s,9H), 1.394 (s, 3H), 1.391 (s, 3H), 1.37-1.12 (m, 6H), 0.82 (s, 9H).¹³C{¹H} NMR (CDCl₃) δ 150.96, 144.22, 142.07, 140.02, 127.49, 126.60,126.56, 123.14, 123.12, 122.96, 116.37, 115.88, 115.72, 110.18, 109.52,97.02, 61.56, 57.03, 38.23, 34.69, 32.41, 32.07, 31.86, 31.72, 31.50,29.98, 25.06, 17.61.

3e. Preparation of3,6-di-tent-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

To a stirred solution of 2.5 g (4.4 mmol) of carbazole derivative, in 40mL of THF, at 0° C., under nitrogen atmosphere, 2.8 mL (7.0 mmol) ofn-butyl lithium (2.5 M solution in hexanes) was added, over a period offive minutes. The solution was stirred at 0° C. for three more hours.2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.44 mL, 7.0 mmol)was added to this, and the stirring continued at 0° C. for one morehour. The reaction mixture was slowly warmed to room temperature, andstirred for 18 hrs. The reaction mixture was concentrated to dryness andby rotary evaporation, and 100 mL of ice cold water was added. Themixture was extracted with methylene chloride. The organic layer waswashed with brine, and dried over anhydrous magnesium sulfate. Removalof the solvent, followed by recrystallization from acetonitrile, gave2.4 g (78.6%) of titled product as white solid. ¹H NMR (CDCl₃) δ8.30-7.96 (m, 2H), 7.81(d, J=2.5 Hz, 1H), 7.58-7.32 (m, 3H), 7.14 (d,J=8.6 Hz, 2H), 4.85 (d, J=2.8 Hz, 1H), 2.76 (td, J=11.0, 2.7 Hz, 1H),2.59 (dd, J=7.9, 3.5 Hz, 1H), 1.73 (s, 2H), 1.67-0.87 (m, 6H), 1.46 (s,9H), 1.45 (s, 9H), 1.38 (s, 9H), 1.37 (s, 9H), 0.78 (s, 9H); ¹³C{¹H} NMR(CDCl₃) δ 156.25, 145.86, 142.05, 142.01, 139.79, 139.78, 133.82,130.61, 129.72, 123.39, 123.37, 123.05, 115.59, 115.55, 110.20, 110.11,101.41, 83.64, 61.20, 56.95, 38.37, 34.68, 32.42, 32.08, 31.90, 31.45,29.97, 25.06, 25.04, 24.79, 18.16. MS m/e 716.38 (M+Na).

3f. Preparation ofmeso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene)

A 2-L, three-neck, round bottom flask, equipped with a thermometer, amagnetic stirrer, an addition funnel, and a nitrogen pad, was chargedwith 2,4-pentanediol (30.46 g, 292.5 mmol, 1 equiv),2-bromo-4-fluorophenol (114.39 g, 598.9 mmol, 2.04 equiv),triphenylphosphine (157.12 g, 599.0 mmol, 2.04 equiv), and THF (600 mL),and the contents cooled to 2° C. in an ice-water bath. A solution ofDIAD (121.11 g, 598.9 mmol, 2.04 equiv) in THF (130 mL), in the additionfunnel, was added, at such a rate, to maintain the reaction below 5° C.(the addition took approximately 4 hours). The resulting mixture wasstirred at 2-° C. for an additional one hour, and a sample was taken forGC-MS analysis, which indicated the reaction was near to completion.After stirring overnight, at ambient temperature, volatiles were removedunder reduced pressure. Cyclohexane (700 mL) was added to the residueand the slurry was stirred at room temperature for 30 minutes. Theinsoluble solid was filtered, rinsed with cyclohexane (100 mL×3). Thecyclohexane solution was washed with 1N NaOH (200 mL), water (200 mL),1N HCl (200 mL), water (500 mL×2), and then concentrated, under reducedpressure, to give an oil residue. The oil residue was dissolved inhexane (100 mL), and then passed through a pad of silica gel (315 g),eluting with hexane (300 mL), and hexane-EtOAc (20:1 in volume, hexane 2L+EtOAc 100 mL), concentrated, and dried, to give the desired bottomgroup (123.8 grams, 94% yield). ¹H NMR (400 MHz, C₆D₆) δ 7.14 (dd,J=8.4, 3.9 Hz, 2H), 6.64 (dt, J=9.1, 3.9 Hz, 2H), 6.48 (dd, J=9.0, 3.7Hz, 2H), 4.22 (m, 2H), 2.17 (dt, J=13.6, 6.5 Hz, 1H), 1.45 (dt, J=13.6,5.6 Hz, 1H), and 0.98 (d, J=6.1 Hz, 6H). ¹³C NMR (101 MHz, CDCl₃) δ156.9 (d, J=235.8 Hz), 150.9 (d, J=2.8 Hz), 120.9 (d, J=25.8 Hz), 115.62(d, J=7.7 Hz), 114.9 (d, J=21.5 Hz), 113.7 (d, J=10.1 Hz), 72.8, 42.7,and 19.6. ¹⁹F NMR (376 MHz, C₆D₆) δ −121.33.

3g. Preparation of Ligand 3 (L3)

Method 1: To a 2 L reactor vessel, was added,meso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (80 g,177.7 mmol) and3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole(271.3 g, 391.0 mmol), dissolved in 800 mL of toluene, under a nitrogenatmosphere, with stirring. To this, was added, NaOH (42.7 g dissolved in100 mL of water, 1.0 mol), followed by quick addition of Pd(PPh₃)₄ (8.21g, 7.11 mmol), and the reaction heated to 88° C. The course of thereaction was monitored via LC, until deemed complete at the five hourmark. At this point, the reaction vessel was cooled to rt (roomtemperature), the caustic layer removed, and 200 mL of a 20% HClsolution was added, and the reaction heated once more to 88° C. for fivehours. The reactor was cooled to ambient temperature, the aqueous layerremoved, and the organic layer washed with brine, and dried over MgSO₄.Filtration to remove the MgSO₄, followed by concentration via rotaryevaporation, gave an off-white solid, which was washed withacetonitrile, and the remaining solid dried under vacuum to provide pureDOC-6163 ligand (199.5 grams, 89% yield).

Method 2 (Two Step Procedure)

Ph₃P (1.05 g, 4 mmol),meso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (45.01g, 100.0 mmol), aliquot 336 (0.326 g) and toluene (500 mL) were addedinto a 2L, three-neck, round bottom flask, equipped with cold watercondenser, magnetic stirrer, a thermometer, and a nitrogen pad in an oilbath. The mixture was sparged with nitrogen for 30 minutes. Pd(OAc)₂(449.02 mg, 2.0 mmol, 0.02 equiv) was added, and the mixture was stirredfor 5-10 minutes, until solid Pd(OAc)₂ dissolved, while sparging withnitrogen. Then 2N NaOH (300 mL, pre-sparged with nitrogen) was added,under nitrogen, and the mixture was sparged with nitrogen for fiveminutes. The reaction mixture was heated to 75-78° C., and a solution of3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole(156.64 g, 220 mmol) in 400 mL of toluene (sparged with nitrogen for 30min) was added, over three hours, via a syringe pump. The reactionmixture was heated at 80-86° C. overnight (the reaction was completeover 4-6 hours, as monitored by LC), under nitrogen atmosphere, in a105° C. oil bath, which resulted in a dark mixture. After being cooledto 50° C., air was bubbled into the reaction mixture for one hour todestroy the catalyst. The reaction mixture was then settled forphase-cut. The bottom aqueous layer was removed, and extracted withtoluene (100 mL). The toluene phase was washed with water (500 mL×2). 2NHCl (300 mL, prepared from 100 mL 6N HCl+200 mL H₂O) was added to thetoluene solution. The resulting mixture was stirred 80-86° C., in a105-108° C. oil bath, under nitrogen overnight. LC analysis of thereaction mixture indicated that the deprotection of the THP group wascomplete. The reaction mixture was allowed to cool to ambienttemperature. The bottom aqueous layer was removed, which wassubsequently extracted with toluene (100 mL). The yellow to browntoluene phase was washed with water (500 mL×2). The toluene solution wasfiltered through a pad of silica gel (60-100 g). The silica gel wet cakewas rinsed with toluene (100 mL). The slightly yellow toluene solutionwas concentrated, under reduced pressure, by rotovap, which gave a thickresidue (185.5 g). Acetonitrile (500 mL) was added to the residue, andthe mixture was spun on roto-vap at 60° C. The thick residue wasgradually dissolved, forming a clear, slightly yellow solution. Whitesolid precipitated out from the solution after a while. After cooling toambient temperature overnight, the solid was collected by filtration,washed/rinsed with acetonitrile (200 mL×2), suck-dried, and dried invacuum oven, to give the desired product (115.5 grams, 92.0% yield). ¹HNMR (400 MHz, C₆D₆) δ 8.45 (t, J=2.4 Hz, 4H), 7.50-7.56 (m, 6H), 7.41(d, J=8.8 Hz, 2H), 7.16 (obscured by CD₅H), 6.32 (s, 2H), 6.30 (dd,J=9.3, 4.7 Hz, 2H), 6.23 (s, 2H), 4.16 (m, 2H), 2.01 (dt, J=14.3, 6.9Hz, 1H), 1.55 (s, 4H), 1.37 (dt, J=14.2, 5.0 Hz, 1H), 1.44 (s, 18H),1.43 (s, 18H), 1.20 (s, 12H), 0.83 (d, J=6.0 Hz, 6H), and 0.80 (s, 18H).¹³C{¹H} NMR (101 MHz, C₆D₆) δ 158.2 (d, J=241.2 Hz), 149.8 (d, J=1.7Hz), 148.9, 143.2, 143.0, 143.0, 140.7 (d, J=5.5 Hz), 131.1 (d, J=7.5Hz), 129.4, 127.2, 126.1, 124.2 (d, J=2.7 Hz), 118.9 (d, J=23.4 Hz),117.3 (d, J=9.2 Hz), 116.8, 115.8 (d, J=22.8 Hz), 110.2 (d, J=10.0 Hz),73.7, 57.1, 42.66, 38.3, 34.9, 32.5, 32.2, 32.1, 31.7, 31.6, and 19.5.¹⁹F NMR (376 MHz, C₆D₆) δ −120.95.

3g. Preparation of Pro-Catalyst 3 (13)

A 5 L reactor was charged with 4.5 L of toluene, and cooled to −30° C.To this, was added, ZrCl₄ (38.81 g, 166.8 mmol), followed by MeMgBr(211.8 mL of a 3M solution, 635.5 mmol). The resulting mixture wasallowed to stir for five minutes, after which, the ligand L3 (199.5 g,158.9 mmol) was added. The suspension was allowed to gradually warm toroom temperature, and was stirred for an additional three hours, andthen filtered. The toluene was then removed, under vacuum, to provide I3as an off white solid in good purity (quantitative, 234 grams). ¹H NMR(400 MHz, C₆D₆) δ 8.53 (m, 2H), 8.41 (dd, J=2.0, 12.0 Hz, 2H), 7.72 (m,2H), 7.67 (d, J=3.0 Hz, 1H), 7.57-7.61 (m, 6H), 7.44 (ddd, J=2.9, 8.1,9.4 Hz, 2H), 7.24 (dd, J=2.0, 14 Hz, 2H), 7.01 (dd, J=3.7, 8.9 Hz, 2H),6.95 (dd, 4.0, 7.3 Hz, 1H), 6.60 (m, 2H), 4.95 (dd, J=4.4, 8.2 Hz, 2H),4.82 (dd, J=4.4, 8.2 Hz, 2H), 4.21 (m, 2H), 3.78 (m, 2H), 1.64 (s, 3H),1.58 (s, 3H), 1.48 (s, 9H), 1.46 (s, 9H), 1.32 (s, 9H), 1.30 (s, 9H),0.77-0.90 (m, 8H), 1.20-1.28 (m, 8H), 0.60 (d, J=7.3 Hz, 3H), 0.41 (d,J=7.3 Hz, 3H), −0.72 (s, 3H), and −0.88 (s, 3H). ¹⁹F NMR (376 MHz, C₆D₆)δ −114.83.

EXAMPLE 4 4a. Preparation of 2-bromo-1-(methoxymethoxy)-4-methylbenzene

2-Bromo-4-methylphenol (13.1 g, 70.0 mmol), dimethoxymethane (35 mL),p-toluene-sulfonic acid (100 mg) and methylene chloride (300 mL) wereheated, under reflux, in a nitrogen atmosphere for three days, using aSoxhlet condenser containing activated 3 Å molecular sieves. Themolecular sieves were exchanged for newly activated ones after every 24hours. The reaction mixture was cooled, and the volatiles were removedby rotary evaporation. The residue was taken up in 100 mL of ether, andwashed successively with 100 mL of 2M sodium hydroxide solution, 100 mLof water and 100 mL of brine. The organic layer was dried over anhydrousmagnesium sulfate and passed through a small bed of silica gel. Removalof the solvent gave 14.5 g (92%) of pure 2, as a pale yellow oil, whichwas used as such for the next step. ¹H NMR (CDCl₃) δ 7.40 (m, 1H), 7.07(m, 2H), 5.25 (s, 2H), 3.55 (s, 3H) and 2.31 (s, 3H).

4c. Preparation of9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole

The 9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)-9H-carbazole(40 g, 0.11 mol) was dissolved in 300 mL of THF, in a nitrogen-filledglovebox, and deprotonated by the slow addition of PhLi (74.6 mL, 0.13mol; 1.8 M in n-Bu₂O). The reaction mixture was stirred for one hour.2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25.1 mL, 0.12 mol)was added slowly, and the reaction mixture was stirred for another hour.Solvent removal, under vacuum, gave an oily residue, which was dissolvedin 450 mL of chloroform, and washed with water (2×450 mL). The organiclayer was dried over MgSO₄, filtered, and the filtrate concentrated,under vacuum, to afford a dark oil, which was then mixed with 600 mLhexane, and concentrated to approximately 250 mL, causing a large amountof light brown solids to form. The solids were filtered and dried undervacuum (42 g, 78%). ¹H NMR (400 MHz, CDCl₃) δ 7.99 (m, 2H), 7.59 (d,J=2.3 Hz, 1H), 7.28 (ddd, J=15.4, 8.2, 1.1 Hz, 2H), 7.14 (m, 5H), 4.78(t, J=3.0 Hz, 1H), 2.44 (m, 2H), 2.25 (s, 3H), 1.59 (m, 1H), 1.28 (s,6H), 1.27 (s, 6H), 1.09 (m, 4H), 0.82 (m, 1H).

4d. Preparation of meso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methylbenzene)

A 2-L, three-neck, round bottom flask, equipped with a thermometer, amagnetic stirrer, and an addition funnel, was charged withmeso-2,4-pentanediol, (30.50 g, 293 mmol), 2-bromo-4-methylphenol(112.03 g, 599 mmol), triphenylphosphine (157.12 g, 599 mmol), and THF(600 mL). The reaction vessel was then placed under a nitrogenatmosphere, and the addition funnel was charged with diisopropylazodicarboxylate (DIAD, 121.11 g, 599 mmol) and THF (250 mL). Thecontents in the flask were cooled to 2° C. in an ice-water bath, theDIAD solution, in the addition funnel, was added, at such a rate, tomaintain the reaction temperature at 2-5° C. (the addition tookapproximately 3.5 hours). The resulting mixture was stirred at 2-5° C.for an additional one hour (a sample was taken for GC-MS analysis, whichshowed the reaction was near to completion), and then allowed to warm upto ambient temperature overnight. The volatiles were removed, underreduced pressure, to give a solid residue (≈424 g). The residue wasextracted with cyclohexane (1000 mL), at 35° C., by spinning on arotary-evaporator for 30 minutes, without pulling vacuum. This processwas repeated for additional three times with cyclohexane (350 mL×3) at35° C. The combined cyclohexane solution was washed with 1N NaOH (350mL×2), water (500 mL), 1N HCl (350 mL), and water (500 mL×2). The washedcyclohexane solution was concentrated to approximately 300 mL, passedthrough a pad of silica gel (350 g), and eluted with hexane/EtOAc (20:1in volume), concentrated, and dried, to give the desired bottom group(119.0 grams, 91.5%). ¹H NMR (400 MHz, CDCl₃) δ 7.26 (d, J=2.3 Hz, 2H),7.04 (dd, J=8.5, 2.3 Hz, 2H), 6.94 (d, J=8.5 Hz, 2H), 4,63 (m, 2H), 2.39(dt, J=13.8, 6.7 Hz, 1H), 2.26 (s, 6H), 1.82 (dt, J=14.1, 5.9 Hz, 1H),and 1.37 (d, J=6.1 Hz, 6H). ¹³C{¹H} NMR (101 MHz, CDCl₃) δ 152.1, 133.9,131.8, 115.2, 114.77, 112.9, 72.5, 42.9, 20.3, and 20.0.

4e. Preparation of Ligand 4 (L4)

To a 2-L reactor vessel, was added,meso-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-methyl-benzene) (40.0g, 90.5 mmol) and9-(5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole(96.2 g, 199.0 mmol, 2.2 equiv), dissolved in 300 mL of toluene, under anitrogen atmosphere, with stirring. To this, was added, NaOH (21.7 gdissolved in 100 mL of water, 0.5 mol, 6 equiv), followed by quickaddition of Pd(PPh₃)₄ (4.18 g, 3.61 mmol, 0.04 equiv). The reaction wasthen heated to 88° C., until complete. The course of the reaction wasmonitored via LC, until deemed complete at the seven hour mark. At thispoint, the reaction vessel was cooled to ambient temperature, thecaustic layer removed, 200 mL of a 20% HCl solution was added, and thereaction heated under reflux for five hours. The reactor was cooled toambient temperature, the stirring was halted, and the aqueous layerremoved. The organic layer washed with brine, dried over MgSO₄, thenfiltered, and concentrated via rotary evaporation, to give an off-whitesolid. The crude residue was washed with acetonitrile and dried undervacuum to provide pure L2 ligand (44.2 grams, 60% yield). ¹H NMR (400MHz, CDCl₃) δ 8.13 (d, J=7.6 Hz, 4H), 7.25 (m, 18H), 6.91 (dd, J=8.3,2.0 Hz, 2H), 6.64 (d, J=8.3 Hz, 2H), 6.30 (s, 2H), 4.45 (m, 2H), 2.41(s, 6H), 2.32 (s, 6H), 2.16 (m, 1H), 1.68 (m, 1H), and 1.14 (d, J=6.1Hz, 6H). ¹³C{¹H} NMR (101 MHz, CDCl₃) δ 151.4, 148.4, 141.4, 141.3,133.1, 131.9, 130.6, 130.1, 129.3, 128.8, 128.0, 125.8, 125.4, 123.4,123.4, 120.3, 119.6, 114.9, 110.4, 110.3, 73.3, 42.7, 20.8, 20.7, and19.9.

4f. Preparation of Pro-Catalyst 4 (14)

A 5 L reactor vessel was charged with 3 L of toluene, and cooled to −30°C. To this, was added, ZrCl₄ (29.6 g, 127 mmol), followed by MeMgBr (161mL of a 3M solution, 484 mmol). The resulting mixture was allowed tostir for five minutes, after which, the ligand (100 g, 121 mmol) wasadded. The suspension was allowed to gradually warm to room temperature,stirred for an additional three hours, and then filtered. The filtratewas concentrated, and analyzed via ¹H NMR spectroscopy, which showed thepresence of I4, but with low purity. The filter cake was then extractedwith methylene chloride (1.5 L), and concentrated, to provide I4 in highpurity (66 grams, 58% yield). ¹H NMR (400 MHz, CDCl₃) δ 8.30 (dd, J=8.5,12.1 Hz, 2H), 8.12 (dd, J=7.4, 10.3 Hz, 2H), 7.57 (d, J=8.25 Hz, 1H),7.26-7.0 (m, 21 H), 6.40 (dd, J=2.2, 8.5 Hz, 1H), 6.30 (dd, J=2.5, 7.15Hz, 1H), 4.44 (d, J=8.1 Hz, 1H), 4.30 (d, J=7.9 Hz, 1H), 4.05 (m, 1H),3.70 (m, 1H), 2.38 (s, 3H), 2.37 (s, 3H), 2.23 (s, 6H), 1.35 (m, 1H),0.59 (d, J=6.8 Hz, 3H), 0.43 (d, J=7.2 Hz, 3H), −1.51 (s, 3H), and −1.68(s, 3H).

EXAMPLE 5 5a. Preparation ofrac-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene)

A 2-L, round bottomed flask, equipped with a magnetic stir, was chargedwith rac-2,4-pentanediol (16.9 g, 162.3 mmol), 2-bromo-4-fluorophenol(65.09 g, 340.8 mmol), triphenyl-phosphine (89.38 g, 340.76 mmol), andTHF (600 mL), and was cooled to 0° C., in an ice-water bath. A solutionof DIAD (67.09 g, 340.76 mmol), in THF (130 mL), was slowly added to theflask, via the addition funnel. The resulting mixture was stirredovernight, at ambient temperature, and the following day, the volatileswere removed under reduced pressure. Pentane (700 mL) was added to theresidue, and the slurry was stirred at room temperature for 30 minutes.The insoluble solid was filtered, rinsed with pentane (100 mL×3), andthen concentrated, under reduced pressure, to give an oil residue. Theoil residue was dissolved in hexane (100 mL), and then passed through apad of silica gel, eluting first with hexane (300 mL), followed byhexane-EtOAc (4:1 in volume), furnishing the desired product in highpurity (42.1 grams, 48% yield). ¹H NMR (400 MHz, CDCl₃): δ 7.20 (dd,J=7.8, 3.0 Hz, 2H), 6.83 (ddd, J=9.1, 7.7, 3.0 Hz, 2H), 6.74 (dd, J=9.1,4.9 Hz, 2H), 4.68 (sextet, J=6.1 Hz, 2H), 2.05 (dd, J=7.3, 5.5 Hz, 2H),and 1.35 (d, J=6.2 Hz, 6H). ¹³C{¹H} NMR (101 MHz, CDCl₃): δ 156.5 (d,J=243.2 Hz), 151.1 (d, J=2.8 Hz), 120.1 (d, J=25.8 Hz), 116.0 (d, J=8.4Hz), 114.8 (d, J=22.7 Hz), 113.3 (d, J=10.1 Hz), 73.4, 44.8, and 20.2.¹⁹F NMR (376 MHz, C₆D₆) δ −121.22.

5e. Preparation of Ligand 5 (L5)

To a vial, was added, therac-4,4′-pentane-2,4-diylbis(oxy))bis(3-bromo-1-fluorobenzene) (0.602 g,1.34 mmol) and the top group (2.04 g, 2.94 mmol) dissolved in 5 mL oftoluene, under a nitrogen atmosphere, with stirring. To this, was added,NaOH (0.321 g dissolved in 1 mL of water, 8.02 mmol), followed by quickaddition of Pd(PPh₃)₄ (0.060 g, 0.054 mmol), and the reaction heated to88° C. The course of the reaction was monitored via LC, until deemedcomplete at the five hour mark. At this point, the reaction vessel wascooled to rt, the caustic layer removed, 2 mL of a 20% HCl solution wasadded, and the reaction heated once more to reflux for five hours. Thereactor was cooled to rt, the aqueous layer removed, and the organiclayer washed with brine, and dried over MgSO₄. Filtration to remove theMgSO₄, followed by concentration via rotary evaporation, gave anoff-white solid, which was washed with acetonitrile, and the remainingsolid dried under vacuum to provide pure L5 (1.41 grams, 84% yield). ¹HNMR (400 MHz, CDCl₃): δ 8.19 (dt, J=3.3, 1.5 Hz, 4H), 7.44 (m, 6H), 7.32(t, J=1.8 Hz, 2H), 7.07 (m, 6H), 6.66 (td, J=8.3, 3.1 Hz, 2H), 6.41 (dd,J=9.2, 4.6 Hz, 2H), 5.91 (s, 2H), 4.36 (m, 2H), 1.74 (s, 4H), 1.71 (m,2H), 1.49 (s, 18H), 1.47 (s, 18H), 1.39 (s, 12H), 0.92 (d, J=5.8 Hz,6H), and 0.80 (s, 18H). ¹³C NMR (101 MHz, CDCl₃): δ 157.5 (d, J=241.3Hz), 150.0 (d, J=1.8 Hz), 147.9, 142.8, 142.6 (d, J=8.4 Hz), 139.8 (d,J=10.9 Hz), 130.2 (d, J=7.8 Hz), 129.0, 127.2, 126.56, 124.8, 123.6 (d,J=13.3 Hz), 123.3, 123.1, 118.2 (d, J=23.4 Hz), 116.4, 116.3, 115.4 (d,J=22.8 Hz), 109.2 (d, J=31.6 Hz), 73.1, 57.0, 44.7, 38.2, 34.7 (d, J=1.6Hz), 32.4, 32.0, 31.9, 31.7, 31.6, and 19.7. ¹⁹F NMR (376 MHz, C₆D₆) δ−121.96.

5e. Preparation of Pro-Catalyst 5 (15)

A flask was charged with 30 mL of cold toluene (−30° C.) and ZrCl4(0.340 grams, 1.50 mmol). To the resulting cold suspension, was added,MeMgBr (1.90 mL of a 3M solution in Et₂O, 5.70 mmol). The resultingmixture was allowed to stir for 2-3 minutes, at which point, the ligandL5 (1.79 grams, 1.43 mmol) was added. The suspension was allowed to warmto room temperature naturally, and was stirred for two hours. Thesolvent was then removed under vacuum, and the dark brown suspension wasextracted with hexanes (100 mL) and filtered. The filtrate wascollected, and dried under vacuum, providing 15 as an off white solid ingood purity (1.46 grams, 75% yield). ¹H NMR (400 MHz, C₆D₆) δ 8.59 (m,2H), 8.40 (m, 2H), 7.79-7.52 (m, 8H), 7.43 (dd, J=8.4, 1.9 Hz, 2H), 7.23(dd, J=12.7, 2.5 Hz, 2H), 6.98 (dt, J=9.0, 3.2 Hz, 2H), 6.66 (ddd,J=8.9, 7.4, 3.2 Hz, 1H), 6.59 (ddd, J=8.9, 7.4, 3.1 Hz, 1H), 5.04 (dd,J=8.9, 5.0 Hz, 1H), 4.88 (dd, J=8.9, 4.9 Hz, 1H), 4.16 (m, 1H), 3.74 (m,1H), 1.80 (m, 1H), 1.67-1.57 (m, 5H), 1.48 (s, 9H), 1.47 (s, 9H), 1.31(s, 9H), 1.30 (s, 9H), 1.28-1.20 (m, 12H), 0.86 (s, 9H), 0.85 (s, 9H),0.59 (d, J=6.4 Hz, 3H), 0.40 (d, J=6.6 Hz, 3H), −0.82 (s, 3H), -0.82 (s,3H). ¹⁹F NMR (376 MHz, C₆D₆) δ −114.59, and −114.68.

Procatalysts used in this study are shown below (Inventive Examples I1,I3 and I4; Comparative Example C11).

Continuous Reactor Ethylene/Octene Copolymerizations

Raw materials (ethylene, 1-octene) and the process solvent (a narrowboiling range high-purity isoparaffinic solvent trademarked SBP 100/140,commercially available from SHELL) are purified with molecular sieves,before introduction into the reaction environment. Hydrogen is suppliedat 1160 psig (80 bar), and reduced to about 580 psig (40 bar); and issupplied as a high purity grade, and is not further purified. Thereactor monomer feed (ethylene) stream is pressurized, via mechanicalcompressor, to above reaction pressure at 525 psig. The solvent andcomonomer (1-octene) feed is pressurized, via mechanical positivedisplacement pump, to above reaction pressure at 525 psig. Modifiedmethylaluminoxane (MMAO), commercially available from AkzoNobel, is usedas an impurity scavenger. The individual catalyst components(procatalyst, cocatalyst) are manually batch diluted, to specifiedcomponent concentrations, with purified solvent (ISOPAR E), andpressurized to 525 psig. The cocatalyst is [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄],commercially available from Boulder Scientific, and is used at a 1.2molar ratio relative to the procatalyst. All reaction feed flows aremeasured with mass flow meters, and independently controlled withcomputer automated valve control systems.

The continuous solution polymerizations are carried out in a 5 L,continuously stirred-tank reactor (CSTR). The reactor has independentcontrol of all fresh solvent, monomer, comonomer, hydrogen, and catalystcomponent feeds. The combined solvent, monomer, comonomer and hydrogenfeed, to the reactor is temperature, controlled, to anywhere from 5° C.to 50° C., and typically 25° C. The fresh comonomer feed to thepolymerization reactor is fed in with the solvent feed. The cocatalystis fed, based on a calculated specified molar ratio (1.2 molarequivalents) to the procatalyst component. Immediately, following eachfresh injection location, the feed streams are mixed, with thecirculating polymerization reactor contents, with static mixingelements. The effluent from the polymerization reactor (containingsolvent, monomer, comonomer, hydrogen, catalyst components, and moltenpolymer) exits the first reactor loop, and passes through a controlvalve (responsible for maintaining the pressure of the first reactor ata specified target). As the stream exits the reactor, it is contactedwith water to stop the reaction. In addition, various additives such asanti-oxidants, can be added at this point. The stream then goes throughanother set of static mixing elements, to evenly disperse the catalystkill and additives.

Following additive addition, the effluent (containing solvent, monomer,comonomer, hydrogen, catalyst components, and molten polymer) passesthrough a heat exchanger, to raise the stream temperature, inpreparation for separation of the polymer from the other lower boilingreaction components. The stream then enters a two stage separation anddevolatization system, where the polymer is removed from the solvent,hydrogen, and unreacted monomer and comonomer. The separated anddevolatized polymer melt is pumped through a die, specially designed forunderwater pelletization, cut into uniform solid pellets, dried, andtransferred into a box for storage.

TABLE 1 Continuous process single reactor polymerization data for 0.3g/10 min (I₂), 0.894-0.896 g/cm³ density resins produced at 150° C. CatEff (MM g I₂ C2 C8 C2 polymer/ H₂ Density (g/10 feed feed Conv Ex. gMetal) (mol %) (g/cm³) min) I₁₀/I₂ (kg/h) (kg/h) (%) Inv 1 (I1) 1.300.16 0.895 0.30 6.1 3.50 3.75 78.6 Inv 2 (I3) 1.70 0.14 0.895 0.33 6.23.50 3.10 78.0 Inv 3 (I3) 1.80 0.15 0.895 0.34 5.9 3.45 3.45 79.4 Inv 4(I4) 1.55 0.13 0.894 0.24 6.1 3.50 4.25 78.8 Comp 1 (C11) 3.80 0.230.896 0.30 7.1 3.50 3.65 78.2

TABLE 2 Continuous process single reactor resin data for 0.2-0.3 g/10min (I₂), 0.894-0.896 g/cm³ density resins produced at 150° C. CEF: peakwidth at 25% peak height Mw Tan delta η₀ Degrees C. Ex. (g/mole) MWD(0.1 rad/s; 190° C.) (Pa · s) ZSVR (° C.) Inv 1 (I1) 140,100 2.0 11.225,889 1.86 9.1 Inv 2 (I3) 135,800 1.9 8.9 25,513 2.05 11.0 Inv 3 (I3)146,200 1.8 11.5 23,441 1.44 11.0 Inv 4 (I4) 142,300 2.0 12.2 31,4912.14 8.4 Comp 1 (C11) 124,600 2.5 4.0 36,212 3.98 8.8

TABLE 3 Continuous process single reactor polymerization data for 0.5g/10 min (I₂) and 0.911-0.914 g/cm³ density resins produced at 150° C.Cat Eff (MM g I₂ C2 C8 C2 polymer/ H₂ Density (g/10 feed feed Conv Ex. gMetal) (mol %) (g/cm³) min) I₁₀/I₂ (kg/h) (kg/h) (%) Inv 5 (I1) 1.400.39 0.912 0.48 5.8 3.91 1.88 79.0 Inv 6 (I3) 2.70 0.35 0.914 0.51 5.63.92 1.35 78.6 Inv 7 (I4) 2.90 0.35 0.911 0.49 5.6 3.91 1.88 78.5 Comp2- (C11) 3.10 0.41 0.913 0.53 6.6 3.91 1.86 78.4

TABLE 4 Continuous process single reactor resin data for 0.5 g/10 min(I₂) and 0.911-0.914 g/cm³ density resins produced at 150° C. CEF: peakwidth at 25% peak height Mw Tan delta η₀ Degrees C. Ex. (g/mole) MWD(0.1 rad/s; 190° C.) (Pa · s.) ZSVR (° C.) Inv 5 (I1) 127,000 1.9 16.015,313 1.57 7.3 Inv 6 (I3) 119,500 2.1 15.4 15,325 1.97 7.4 Inv 7 (I4)125,000 1.9 21.0 15,015 1.64 6.0 Comp 2 (C11) 114,300 2.0 5.9 19,4932.94 6.2

TABLE 5 Continuous process single reactor polymerization data for 1 g/10min (I₂), and 0.912-0.914 g/cm³ density resins produced at 150° C. CatEff I₂ C2 C8 C2 (MM g H₂ Density (g/10 feed feed Conv Example poly/g M)(mol %) (g/cm³) min) I₁₀/I₂ (kg/h) (kg/h) (%) Inv 8 (I1) 1.30 0.49 0.9120.93 5.7 3.91 1.91 78.7 Inv 9 (I3) 2.10 0.45 0.913 1.02 5.5 4.39 1.7978.9 Inv 10 (I4) 3.00 0.41 0.914 1.05 5.5 3.91 2.00 78.6 Comp 3 (C11)3.60 0.51 0.912 1.08 6.2 3.91 2.10 78.4

TABLE 6 Continuous process single reactor resin data for 1 g/10 min(I₂), and 0.912-0.914 g/cm³ density resins produced at 150° C. CEF: peakwidth at Mw Tan delta η₀ 25% peak height Ex. (g/mole) MWD (0.1 rad/s;190° C.) (Pa · s) ZSVR (° C.) Inv 8 (I1) 107,600 2.0 36.1 7,923 1.49 7.9Inv 9 (I3) 108,500 1.9 30.1 7,361 1.34 8.9 Inv 10 (I4) 99,900 1.9 44.26,821 1.68 6.8 Comp 3 (C11) 96,100 2.1 13.0 8,045 2.29 7.2 Comp 4*113,632 2.3 54.2 6,949 1.07 35.7 *Comp 4 is EXCEED 1012 available fromExxonMobil.

As seen in Tables 1-6, the inventive ethylene-based polymers have aunique combination of structural properties, characterized by low levelsof long chain branching, low zero shear viscosity ratio, optimal tandelta, narrow comonomer distribution (CEF profile; each inventivepolymer had a single peak, in the CEF-Comonomer Distribution, at atemperature from 60° C. to 100° C. (see Tables 2, 4 and 6 for the “peakwidth at 25% peak height”)), and narrow molecular weight distribution.The inventive polymers would be useful for the fabrication of moldedarticles with improved properties (for example, optical properties, dartdrop impact resistance, puncture resistance, crack resistance, etc.).

Test Methods Density

Samples that are measured for density are prepared according to ASTMD-1928. Measurements are made within one hour of sample pressing usingASTM D-792, Method B.

Melt Index

Melt index (I₂) is measured in accordance with ASTM-D 1238, Condition190° C./2.16 kg, and is reported in grams eluted per 10 minutes. Meltflow rate (I₁₀) is measured in accordance with ASTM-D 1238, Condition190° C./10 kg, and is reported in grams eluted per 10 minutes.

Conventional Gel Permeation Chromatography (conv. GPC)

A GPC-IR high temperature chromatographic system from, PolymerChAR(Valencia, Spain), was equipped with a Precision Detectors (Amherst,MA), 2-angle laser light scattering detector Model 2040, an IRSinfra-red detector and a 4-capillary viscometer, both from PolymerChAR.Data collection was performed using PolymerChAR InstrumentControlsoftware and data collection interface. The system was equipped with anon-line, solvent degas device and pumping system from AgilentTechnologies (Santa Clara, Calif.).

Injection temperature was controlled at 150 degrees Celsius. The columnsused were three 10-micron “Mixed-B” columns from Polymer Laboratories(Shropshire, UK). The solvent used was 1,2,4-trichlorobenzene. Thesamples were prepared at a concentration of “0.1 grams of polymer in 50milliliters of solvent.” The chromatographic solvent and the samplepreparation solvent each contained “200 ppm of butylated hydroxytoluene(BHT).” Both solvent sources were nitrogen sparged. Ethylene-basedpolymer samples were stirred gently at 160 degrees Celsius for threehours. The injection volume was 200 microliters, and the flow rate was 1milliliters/minute. The GPC column set was calibrated by running 21“narrow molecular weight distribution” polystyrene standards. Themolecular weight (MW) of the standards ranged from 580 to 8,400,000g/mole, and the standards were contained in six “cocktail” mixtures.Each standard mixture had at least a decade of separation betweenindividual molecular weights. The standard mixtures were purchased fromPolymer Laboratories. The polystyrene standards were prepared at “0.025g in 50 mL of solvent” for molecular weights equal to, or greater than,1,000,000 g/mole, and at “0.050 g in 50 mL of solvent” for molecularweights less than 1,000,000 g/mole.

The polystyrene standards were dissolved at 80° C., with gentleagitation, for 30 minutes. The narrow standards mixtures were run first,and in order of decreasing “highest molecular weight component,” tominimize degradation. The polystyrene standard peak molecular weightswere converted to polyethylene molecular weight using Equation 1 (asdescribed in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621(1968)):

Mpolyethylene=A×(Mpolystyrene)^(B)   (Eqn. 1),

where M is the molecular weight, A is equal to 0.4316 and B is equal to1.0.

Number-average molecular weight (Mn(conv gpc)), weight average molecularweight (Mw-conv gpc), and z-average molecular weight (Mz(conv gpc)) werecalculated according to Equations 2-4 below:

$\begin{matrix}{{{{Mn}\left( {{conv}\mspace{14mu} {gpc}} \right)} = \frac{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( {IR}_{{measurement}\mspace{14mu} {channel}_{i}} \right)}{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( \frac{{IR}_{{measurement}\mspace{14mu} {channel}_{i}}}{M_{{PE}_{i}}} \right)}},} & \left( {{Eqn}.\mspace{11mu} 2} \right) \\{{{{Mw}\left( {{conv}\mspace{14mu} {gpc}} \right)} = \frac{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( {M_{{PE}_{i}}{IR}_{{measurement}\mspace{14mu} {channel}_{i}}} \right)}{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( {IR}_{{measurement}\mspace{14mu} {channel}_{i}} \right)}},} & \left( {{Eqn}.\mspace{11mu} 3} \right) \\{{{Mz}\left( {{conv}\mspace{14mu} {gpc}} \right)} = {\frac{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( {M_{{PE}_{i}}^{2}{IR}_{{measurement}\mspace{14mu} {channel}_{i}}} \right)}{\Sigma_{i = {RV}_{{integration}\mspace{14mu} {start}}}^{i = {RV}_{{integration}\mspace{14mu} {end}}}\left( {M_{{PE}_{i}}{IR}_{{measurement}\mspace{14mu} {channel}_{i}}} \right)}.}} & \left( {{Eqn}.\mspace{11mu} 4} \right)\end{matrix}$

In Equations 2-4, the RV is column retention volume (linearly-spaced),collected at “1 point per second,” the IR is the baseline-subtracted IRdetector signal, in Volts, from the IRS measurement channel of the GPCinstrument, and M_(PE) is the polyethylene-equivalent MW determined fromEquation 1. Data calculations were performed using “GPC One software(version 2.013H)” from PolymerChAR.

Creep Zero Shear Viscosity Measurement Method

Zero-shear viscosities were obtained via creep tests, which wereconducted on an AR-G2 stress controlled rheometer (TA Instruments; NewCastle, Del.), using “25-mm-diameter” parallel plates, at 190° C. Therheometer oven was set to test temperature for at least 30 minutes,prior to zeroing the fixtures. At the testing temperature, a compressionmolded sample disk was inserted between the plates, and allowed to cometo equilibrium for five minutes. The upper plate was then lowered downto 50 μm (instrument setting) above the desired testing gap (1.5 mm).Any superfluous material was trimmed off, and the upper plate waslowered to the desired gap. Measurements were done under nitrogenpurging at a flow rate of 5 L/min. The default creep time was set fortwo hours.

Each sample was compression-molded into “2 mm thick×25 mm diameter”circular plaque, at 177° C., for five minutes, under 10 MPa pressure, inair. The sample was then taken out of the press and placed on a countertop to cool.

A constant low shear stress of 20 Pa was applied for all of the samples,to ensure that the steady state shear rate was low enough to be in theNewtonian region. The resulting steady state shear rates were in therange from 10⁻³ to 10⁻⁴ s⁻¹ for the samples in this study. Steady statewas determined by taking a linear regression for all the data, in thelast 10% time window of the plot of “log(J(t)) vs. log(t),” where J(t)was creep compliance and t was creep time. If the slope of the linearregression was greater than 0.97, steady state was considered to bereached, then the creep test was stopped. In all cases in this study,the slope meets the criterion within two hours. The steady state shearrate was determined from the slope of the linear regression of all ofthe data points, in the last 10% time window of the plot of “ε vs. t,”where c was strain. The zero-shear viscosity was determined from theratio of the applied stress to the steady state shear rate.

In order to determine if the sample was degraded during the creep test,a small amplitude oscillatory shear test was conducted before, andafter, the creep test, on the same specimen from 0.1 to 100 rad/s. Thecomplex viscosity values of the two tests were compared. If thedifference of the viscosity values, at 0.1 rad/s, was greater than 5%,the sample was considered to have degraded during the creep test, andthe result was discarded.

Zero-Shear Viscosity Ratio (ZSVR) is defined as the ratio of thezero-shear viscosity (ZSV) of the branched polyethylene material to theZSV of a linear polyethylene material (see ANTEC proceeding below) atthe equivalent weight average molecular weight (Mw(conv gpc)), accordingto the following Equation 5:

$\begin{matrix}{{ZSVR} = {\frac{\eta_{0B}}{\eta_{0L}} = {\frac{\eta_{0B}}{2.29^{- 15}M_{w{({{conv} \cdot {gpc}})}}^{3.65}}.}}} & \left( {{Eqn}.\mspace{11mu} 5} \right)\end{matrix}$

The ZSV value was obtained from creep test, at 190° C., via the methoddescribed above. The Mw(conv gpc) value was determined by theconventional GPC method (Equation 3), as discussed above. Thecorrelation between ZSV of linear polyethylene and its Mw(conv gpc) wasestablished, based on a series of linear polyethylene referencematerials. A description for the ZSV-Mw relationship can be found in theANTEC proceeding: Karjala et al., Detection of Low Levels of Long-chainBranching in Polyolefins, Annual Technical Conference—Society ofPlastics Engineers (2008), 66th 887-891.

CEF Method

Comonomer distribution analysis was performed with CrystallizationElution Fractionation (CEF) (PolymerChAR in Spain (see also B Monrabalet al, Macromol. Symp., 257, 71-79,2007). Ortho-dichlorobenzene (ODCB)with “600 ppm antioxidant butylated hydroxytoluene (BHT)” was used assolvent. Sample preparation was done with auto sampler at 160° C., fortwo hours, under shaking at 4 mg/ml (unless otherwise specified). Theinjection volume was 300 μl. The temperature profile of CEF was asfollows: crystallization at 3° C./min from 110° C. to 30° C.; thermalequilibrium at 30° C. for five minutes; elution at 3° C./min from 30° C.to 140° C. The flow rate during crystallization was at 0.052 ml/min. Theflow rate during elution was at 0.50 ml/min. The data was collected atone data point/second.

CEF column was packed with glass beads at 125 μm±6% (MO-SCI SpecialtyProducts) using ⅛ inch stainless tubing. Glass beads were acid washed byMO-SCI Specialty. The column volume was 2.06 ml. The column temperaturecalibration was performed using a mixture of NIST Standard ReferenceMaterial Linear polyethylene 1475a (1.0 mg/ml), and Eicosane (2 mg/ml)in ODCB. The temperature was calibrated by adjusting elution heatingrate, so that the NIST linear polyethylene 1475a had a peak temperatureat 101.0° C., and Eicosane had a peak temperature of 30.0° C. The CEFcolumn resolution was calculated with a mixture of the NIST linearpolyethylene 1475a (1.0 mg/ml) and hexacontane (Fluka, purum, ≧97.0%, 1mg/ml). A baseline separation of hexacontane and NIST polyethylene 1475awas achieved. The area of hexacontane (from 35.0 to 67.0° C.) to thearea of NIST 1475a (from 67.0 to 110.0° C.) was “50 to 50,” the amountof soluble fraction below 35.0° C. was less than (<) 1.8 wt %. The CEFcolumn resolution was defined in Equation 1A, where the columnresolution was 6.0.

$\begin{matrix}{{Resolution} = {\frac{\begin{matrix}{{{Peak}\mspace{14mu} {temperature}\mspace{14mu} {of}\mspace{14mu} {NIST}\mspace{14mu} 1475a} -} \\{{Peak}\mspace{14mu} {Temperature}\mspace{14mu} {of}\mspace{14mu} {Hexacontane}}\end{matrix}}{\begin{matrix}{{{Half}\text{-}{height}\mspace{14mu} {Width}\mspace{14mu} {of}\mspace{14mu} {NIST}\mspace{14mu} 1475a} +} \\{{Half}\text{-}{height}\mspace{14mu} {Width}\mspace{14mu} {of}\mspace{14mu} {Hexacontane}}\end{matrix}}.}} & \left( {{{Eqn}.\mspace{11mu} 1}A} \right)\end{matrix}$

Determination of Peak Width at 25 Percent Height of the CEF ElutionProfile

The CEF instrument was calibrated according to the CEF Method describedherein, and a plot of the relative IR detector signal was made as afunction of temperature. A single baseline was subtracted from the IRmeasurement signal, in order create a relative mass-elution profileplot, starting, and ending, at zero relative mass at its lowest andhighest elution temperatures (typically between 25° C. and 110° C.). Inthe relative mass-elution profile plot, the peak that represents an areaof at least 50% of the total integrated signal between 35° C. and 95° C.degrees was assigned. If the peak did not return to the baseline by atleast 10% of the relative mass-elution height (connected by more than10% height at their lowest point), it was defined as part of the singlepeak (no deconvolution or similar numerical methods are used tomathematically separate convoluted peaks). The peak was then measuredfor width in, ° C., at 25% of the maximum height of the peak in themass-elution profile plot.

Dynamic Shear Rheology

Each sample was compression-molded into “3 mm thick×25 mm diameter”circular plaque, at 177° C., for five minutes, under 10 MPa pressure, inair. The sample was then taken out of the press, and placed on a countertop to cool. Constant temperature, frequency sweep measurements wereperformed on an ARES strain controlled rheometer (TA Instruments),equipped with “25 mm” parallel plates, under a nitrogen purge. For eachmeasurement, the rheometer was thermally equilibrated for at least 30minutes, prior to zeroing the gap. The sample disk was placed on theplate, and allowed to melt for five minutes at 190° C. The plates werethen closed to 2 mm, the sample trimmed, and then the test was started.The method had an additional five minute delay built in, to allow fortemperature equilibrium. The experiments were performed at 190° C., overa frequency range from 0.1 to 100 rad/s, at five points per decadeinterval. The strain amplitude was constant at 10%. The stress responsewas analyzed in terms of amplitude and phase, from which the storagemodulus (G′), loss modulus (G″), complex modulus (G*), dynamic viscosity(η* or Eta*), and tan δ (or tan delta) were calculated.

The present invention may be embodied in other forms, without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

1. An ethylene-based polymer comprising the following properties: a) aZSVR value from 1.2 to 2.6, b) a MWD from 1.5 to 2.8, and c) a tan delta(0.1 rad/s; 190° C.) from 5.0 to
 50. 2. The ethylene-based polymer ofclaim 1, wherein the ethylene-based polymer has the followingproperties: a melt index (I2) less than 0.9 g/10 min, and a tan delta(0.1 rad/s; 190° C.) greater than 5.0.
 3. The ethylene-based polymer ofclaim 1, wherein the ethylene-based polymer has the followingproperties: a melt index (I2) greater than, or equal to, 0.9 g/10 min,and a tan delta (0.1 rad/s; 190° C.) greater than 15; and a ZSVR valuefrom 1.3 to 2.6.
 4. The ethylene-based polymer of claim 1, wherein theethylene-based polymer is an ethylene/alpha-olefin interpolymer.
 5. Theethylene-based polymer of claim 1, wherein the polymer has a densityfrom 0.885 to 0.940 g/cc.
 6. The ethylene-based polymer of claim 1,wherein the polymer has a melt index (I2) from 0.05 to 500 g/10 min. 7.The ethylene-based polymer of claim 1, wherein the polymer has a singlepeak in the CEF-Comonomer Distribution, at a temperature from 60° C. to100° C.
 8. The ethylene-based polymer of claim 1, wherein the polymerhas a single peak in the CEF-Comonomer Distribution, at a temperaturefrom 60 to 100° C., and wherein the peak width at 25% peak height isless than 30° C.
 9. The ethylene-based polymer of claim 1, wherein thepolymer has an I₁₀/I₂ ratio from 5.0 to
 10. 10. The ethylene-basedpolymer of claim 1, wherein the polymer has a MWD from 1.7 to 2.5. 11.The ethylene-based polymer of claim 1, wherein the polymer has a meltindex (I2) from 0.1 to 5 g/10 min.
 12. The ethylene-based polymer ofclaim 1, wherein the ethylene-based polymer is formed by a processcomprising polymerizing at least ethylene, in the presence of at leastone catalyst system comprising the reaction product of the following: A)at least one cocatalyst; and B) a procatalyst comprising a metal-ligandcomplex of Formula (I):

wherein: M is titanium, zirconium, or hafnium, each independently beingin a formal oxidation state of +2, +3, or +4; and n is an integer from 0to 3, and wherein when n is 0, X is absent; and Each X, independently,is a (C₁-C₄₀)hydrocarbyl, a (C₁-C₄₀)heterohydrocarbyl, or a halide, andwherein each X, independently, is a monodentate ligand that is neutral,monoanionic, or dianionic; or wherein two Xs are taken together to forma bidentate ligand that is neutral, monoanionic, or dianionic; andwherein X and n are chosen, in such a way, that the metal-ligand complexof Formula (I) is, overall, neutral; and Each Z, independently, is anoxygen atom, a sulfur atom, —N[(C₁-C₄₀)hydrocarbyl]-, or—P[(C₁-C₄₀)hydrocarbyl]-; and L is a substituted or unsubstituted(C₁-C₄₀)hydrocarbylene, or a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbylene, and wherein, for L, the(C₁-C₄₀)hydrocarbylene has a portion that comprises a 1-carbon atom to10-carbon atom linker backbone linking R²¹ and R²² in Formula (I) (towhich L is bonded), or wherein, for L, the (C₁-C₄₀)heterohydrocarbylenehas a portion that comprises a 1-atom to 10-atom linker backbone linkingR²¹ and R²² in Formula (I), wherein each of the 1 to 10 atoms of the1-atom to 10-atom linker backbone of the (C₁-C₄₀)heterohydrocarbylene,independently, is one of the following: i) a carbon atom, ii) aheteroatom, wherein each heteroatom independently is —O— or —S—, or iii)a substituent selected from —S(O)—, —S(O)₂—, —Si(R^(C))₂—, —Ge(R^(C))₂—,—P(R^(C))—, or —N(R^(C))—, and wherein each R^(C) is, independently, asubstituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted orunsubstituted (C₁-C₃₀) hetero-hydrocarbyl; and R²¹ and R²² are each,independently, C or Si; and R¹ through R²⁰ are each, independently,selected from the group consisting of the following: a substituted orunsubstituted (C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)hetero-hydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, and a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and wherein,when R¹⁷ is a hydrogen atom, then R¹⁸ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or wherein,when R¹⁸ is a hydrogen atom, then R¹⁷ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and/or wherein,when R¹⁹ is a hydrogen atom, then R²⁰ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or wherein,when R²⁰ is a hydrogen atom, then R¹⁹ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,a halogen atom, or a hydrogen atom; and wherein each R^(C) isindependently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; and wherein,for Formula I, two or more of R¹ through R²², optionally, may form oneor more ring structures, and wherein each ring structure has from 3 to50 atoms in the ring, excluding any hydrogen atoms; and wherein, forFormula I, one or more hydrogen atoms may optionally be substituted withone or more deuterium atoms.
 13. The ethylene-based polymer of claim 12,wherein, for Formula I, wherein when R¹⁷ is a hydrogen atom, then R¹⁸ isa substituted or unsubstituted (C₁-C₄₀)hydrocarbyl, a substituted orunsubstituted (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃,—P(R^(C))₂, —N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C),—S(O)₂R^(C), —N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C),—C(O)N(R^(C))₂, or a halogen atom; and wherein each R^(C) is independently a substituted or unsubstituted (C₁-C₃₀)hydrocarbyl, or asubstituted or unsubstituted (C₁-C₃₀) heterohydrocarbyl; or wherein,when R¹⁸ is a hydrogen atom, then R¹⁷ is a substituted or unsubstituted(C₁-C₄₀)hydrocarbyl, a substituted or unsubstituted(C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃, —Ge(R^(C))₃, —P(R^(C))₂,—N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C), —S(O)₂R^(C),—N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂,or a halogen atom; and wherein each R^(C) is independently a substitutedor unsubstituted (C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted(C₁-C₃₀) heterohydrocarbyl; and/or wherein, when R¹⁹ is a hydrogen atom,then R²⁰ is a substituted or unsubstituted (C₁-C₄₀)hydrocarbyl, asubstituted or unsubstituted (C₁-C₄₀)heterohydrocarbyl, —Si(R^(C))₃,—Ge(R^(C))₃, —P(R^(C))₂, —N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃,—S(O)R^(C), —S(O)₂R^(C), —S(O)₂R^(C), —N═C(R^(C))₂, —OC(O)R^(C),—C(O)OR^(C), —N(R)C(O)R^(C), —C(O)N(R^(C))₂, or a halogen atom; andwherein each R^(C) is independently a substituted or unsubstituted(C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted (C₁-C₃₀)heterohydrocarbyl; or wherein, when R²⁰ is a hydrogen atom, then R¹⁹ isa substituted or unsubstituted (C₁-C₄₀)hydrocarbyl, a substituted orunsubstituted (C₁-C₄₀)heterohydrocarbyl,—Si(R^(C))₃, —Ge(R^(C))₃,—P(R^(C))₂, —N(R^(C))₂, —OR^(C), —SR^(C), —NO₂, —CN, —CF₃, —S(O)R^(C),—S(O)₂R^(C), —S(O)₂R^(C), —N═C(R^(C))₂, —OC(O)R^(C), —C(O)OR^(C),—N(R)C(O)R^(C), —C(O)N(R^(C))₂, _(or a) h_(a)lo_(g)en atom; and whereineach R^(C) is independently a substituted or unsubstituted(C₁-C₃₀)hydrocarbyl, or a substituted or unsubstituted (C₁-C₃₀)heterohydrocarby
 14. A composition comprising the ethylene-based polymerof claim
 1. 15. An article comprising at least one component formed fromthe composition of claim 14.